Metallocene complex and catalyst prepared therefrom

Abstract

A racemic metallocene complex of formula (I'), wherein each X is a sigma donor ligand; L is a divalent bridge based on carbon, silicon or germanium, wherein one or two main chain atoms are connected to the ligand; M is Ti, Zr or Hf; each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S; each R1 is the same or different and is a straight chain C 1‑10 Alkyl, or straight chain C 1‑10 Alkoxy, each n is 0-3; each R2 is the same or different and is a -Si(RaRbRc) group; Ra is optionally substituted by 1-3 C 1‑6 Alkyl substituted C 1‑10 alkyl or phenyl; Rb is optionally substituted by 1-3 C 1‑6 Alkyl substituted C 1‑10 Alkyl or phenyl; Rc is optionally substituted by 1-3 C 1‑6 alkyl-substituted phenyl; and each p is 1‑3.

Description

[0001] The present invention relates to certain novel metallocene complexes and catalysts prepared therefrom. The present invention also relates to methods for preparing these catalysts. Finally, the present invention relates to methods for preparing olefin polymers, such as polyethylene or polypropylene polymers, especially polyethylene polymers, using the metallocene catalysts. In particular, the catalysts used in the present invention are catalysts that can be prepared in a one-step or two-step catalyst preparation process. Background Art

[0002] In a multistage polymerization for the preparation of multimodal polymers, different polymer fractions are produced continuously in each reactor. Typically, a lower molecular weight polymer fraction is produced in the first reactor and a higher molecular weight polymer fraction is produced in a subsequent reactor. Control of the fractions can also be applied to comonomer content, branching, comonomer type, etc.

[0003] The use of multiple reactors with different conditions (physical and chemical) places stringent demands on the catalyst system used, since the same catalyst system is usually used for all stages of the polymerization. The catalyst is usually transferred from the first stage to the second stage and therefore needs to function in all stages of the reaction. The catalyst needs to remain stable for the entire duration of the multi-stage process. The catalyst needs to operate under the different conditions provided, which include slurry and gas phase polymerization.

[0004] The catalyst must be able to produce polymers of lower molecular weight as well as higher molecular weight. The catalyst must perform well in ethylene homopolymerization and / or polymerization reactions with low comonomer concentrations as well as polymerization reactions with high comonomer concentrations (see AR Albunia, F. Prades and D. Jeremic, Ed., Multimodal Polymers with Supported Catalysts, Springer 2019, ISBN 978-3-030-03474-0).

[0005] Typically, Ziegler-Natta catalysts have been used in multistage systems with very good results, but these catalysts do not allow for very specific polymer architectures. On the other hand, single-site catalysts such as metallocenes allow for very controlled polymer architectures. However, combining the advantages of single-site catalysis with those of multistage processes has been very challenging, as it has been difficult to find metallocene catalysts with the desired properties, namely:

[0006] - The catalyst must have good kinetic stability, since the catalyst must polymerize over an average residence time of several hours under different reaction conditions,

[0007] - The catalyst must be able to produce lower M in different reactors wand higher M w polymers;

[0008] - The catalyst must have high catalytic activity in all reactors.

[0009] The present inventors therefore sought a metallocene catalyst for multistage polymerization which could provide multimodal polymers, for example:

[0010] - High molecular weight;

[0011] -High comonomer content;

[0012] - good catalyst activity; and

[0013] -Ability to make lower and higher M in cascade w Component (which is M through hydrogen w regulators promote).

[0014] Particularly preferably, the activity of the catalyst in the gas phase is high relative to the slurry phase, i.e. the ratio of gas phase activity / slurry phase activity is high, e.g. the ratio is 1.8 or above. Thus, it is highly preferred if the activity of the catalyst in the gas phase is higher than the activity in the slurry phase, e.g. the ratio of gas phase activity / slurry phase activity is 1.8-10, especially 2-8, more preferably 2.2-6.

[0015] It would also be desirable to provide catalysts that offer value in unimodal polymerisations, for example for polyethylene or polypropylene. In particular, high catalyst activity (especially in slurry) and good comonomer incorporation are important for ethylene polymerisation.

[0016] Good M w Capacity and stable reaction kinetics are also a goal. Higher activity and improved comonomer sensitivity with higher M w This combination of capabilities is critical to the economic viability of a catalyst.

[0017] In propylene polymerization, it is important to w It is also desirable to preferably have a good powder morphology with good isotacticity, low soluble components and high melting temperature.

[0018] Surprisingly, it has now been found that certain bridged biscyclopentadienyl-type complexes having heterocyclic substituents such as furanyl moieties provide desirable properties, particularly when supported on a support.

[0019] Specifically, the complexes of the present invention show higher activity and advanced M w When H2 is added to the polymerization, it is possible to control the M wThe catalysts of the present invention are highly favored for their ability to be used in both single-stage and multi-stage process settings due to their stable kinetic profiles in the slurry phase, similar or higher activity in the gas phase, and higher gas-phase to slurry-phase activity ratios.

[0020] The present inventors have identified a catalyst having high catalyst activity, high comonomer incorporation and higher M w The combination of these effects and improved performance makes the catalysts of the present invention particularly valuable.

[0021] US6326493 describes certain furanyl-containing metallocene catalysts, but not those claimed herein.

[0022] JP 2016 / 183334 describes a multimodal polyethylene-based resin comprising two multimodal polyethylene resins (C) and (G). The multimodal polyethylene is produced in a multistage process. SUMMARY OF THE INVENTION

[0023] Therefore, from one aspect, the present invention provides a racemic metallocene complex of formula (I')

[0024]

[0025] wherein each X is a σ-donating ligand;

[0026] L is a divalent bridge based on carbon, silicon or germanium, in which one or two backbone atoms are connected to the ligand;

[0027] M is Ti, Zr or Hf;

[0028] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0029] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0030] Each n is 0-3;

[0031] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0032] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl;

[0033] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10Alkyl or phenyl;

[0034] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted phenyl;

[0035] Each p is 1-3.

[0036] From another aspect, the present invention provides a racemic metallocene complex of formula (Ia)

[0037]

[0038] wherein each X is a σ-donating ligand;

[0039] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0040] L is a (RdRe)Si group, a (RdRe)Ge group or a (RdRe)CH2 group;

[0041] Rd is C 1-10 Alkyl, C 5-10 cycloalkyl, benzyl or phenyl;

[0042] Re is C 2-10 alkenyl;

[0043] M is Ti, Zr or Hf;

[0044] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0045] Each n is 0-3;

[0046] Each R2 is the same or different and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0047] Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and

[0048] Each p is 0-3.

[0049] From another aspect, the present invention provides a racemic metallocene complex of formula (Ia')

[0050]

[0051] wherein each X is a σ-donating ligand;

[0052] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0053] L is a (RdRe)Si group;

[0054] Rd is C 1-10 alkyl;

[0055] Re is C 2-10 alkenyl;

[0056] M is Ti, Zr or Hf;

[0057] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0058] Each n is 0-3;

[0059] Each R2 is the same or different and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0060] Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and

[0061] Each p is 0-3.

[0062] From another aspect, the present invention provides a metallocene catalyst comprising:

[0063] (i) a complex of formula (I') or formula (Ia) as defined above;

[0064] (ii) a promoter comprising a compound of a Group 13 element; and optionally

[0065] (iii) Vector.

[0066] Viewed from another aspect the invention provides a process for the preparation of an olefin polymer such as a polyethylene or polypropylene polymer comprising polymerising at least one olefin in the presence of a metallocene catalyst as hereinbefore defined.

[0067] Viewed from another aspect the invention provides a process for the preparation of polyethylene comprising polymerising ethylene and optionally at least one C 4-10 Alpha olefin comonomer.

[0068] Viewed from another aspect the invention provides a process for preparing a multimodal polyethylene polymer comprising:

[0069] (I) In a first stage, ethylene and optionally at least one C 4-10 an alpha olefin comonomer to form a first polyethylene component (e.g., a lower molecular weight component);

[0070] (i) a metallocene complex of formula (I') or (Ia) as defined above;

[0071] (ii) a promoter comprising a compound of a Group 13 element; and optionally

[0072] (iii) a carrier;

[0073] (II) in a second stage, polymerizing ethylene and optionally at least one C 4-10 The alpha olefin comonomer is polymerized to form a second polyethylene component (eg, a higher molecular weight component).

[0074] Viewed from another aspect the invention provides the use of a metallocene catalyst as hereinbefore defined in a process comprising a slurry phase step and a gas phase step for preparing olefin polymers, such as polyethylene or polypropylene polymers, especially multimodal ethylene polymers.

[0075] definition

[0076] The following definitions apply throughout the specification.

[0077] Unless otherwise specified, the term "molecular weight" as used herein refers to the weight average molecular weight M w .

[0078] Detailed description of the invention

[0079] The present invention relates to a metallocene complex for olefin polymerization and a catalyst prepared therefrom. The present invention further relates to a method for preparing an olefin polymer, such as a polypropylene or polyethylene polymer, using the metallocene catalyst.

[0080] Metallocene

[0081] The metallocene complexes used in the present invention can be symmetrical or asymmetrical. In simple terms, "asymmetrical" means that the two ligands forming the metallocene complex are different, i.e., each ligand carries a set of chemically different substituents. The term "symmetrical" means that the two ligands in the metallocene complex are the same, i.e., they have the same substituent pattern.

[0082] The metallocene catalyst complex of the present invention is racemic. Therefore, the metallocene catalyst complex of the present invention should be the trans configuration of the chiral, racemic bridged biscyclopentadienyl metallocene complex.

[0083] In addition to the racemic isomers, the metallocene catalysts of the present invention may also include some meso or cis isomers. Due to the synthetic nature of metallocene complexes, these metallocene complexes may be produced as mixtures. Up to 60 mol% of the meso isomer may be present in such a mixture, so at least 40 mol% of the racemic isomer may be present in such a mixture.

[0084] However, preferably, the content of the racemic isomer is 50 mol% or more, such as 60 mol% or more, especially 70 mol% or more, ideally 90 mol% or more, based on the entire weight of the complex.

[0085] Metallocene complexes can be C2 symmetry or C1 symmetry. When they are C1 symmetry, they still keep pseudo-C2 symmetry, because although they do not keep symmetry in the ligand periphery, they still keep C2 symmetry near the metal center. According to their chemical properties, in the building-up process of complex, meso form and racemic enantiomer pair (in the case of complex C2 symmetry) or trans and cis enantiomer pair (in the case of complex C1 symmetry) can be formed. For the purpose of the present invention, "racemic-trans" refers to that two ligands are oriented in opposite directions relative to cyclopentadienyl-metal-cyclopentadienyl plane, and "racemic-cis" refers to that two ligands are oriented in the same direction relative to cyclopentadienyl-metal-cyclopentadienyl plane.

[0086] The metallocene catalyst complex of the present invention includes the racemic trans isomer. Therefore, ideally, at least 95 mol%, such as at least 98 mol%, especially at least 99 mol% of the metallocene catalyst complex is the racemic trans isomer.

[0087] The following preferences apply to the metallocene catalyst complex of the present invention. The complex of the present invention may have the structure of formula (I'):

[0088]

[0089] wherein each X is a σ-donating ligand;

[0090] L is a divalent bridge based on carbon, silicon or germanium, in which one or two backbone atoms are connected to the ligand;

[0091] M is Ti, Zr or Hf;

[0092] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0093] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0094] Each n is 0-3;

[0095] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0096] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl;

[0097] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl;

[0098] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted phenyl;

[0099] Each p is 1-3;

[0100] Racemic metallocene complex of formula (Ia)

[0101]

[0102] wherein each X is a σ-donating ligand;

[0103] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0104] L is a (RdRe)Si group, (RdRe)Ge or (RdRe)CH2;

[0105] Rd is C 1-10 Alkyl, C 5-10 cycloalkyl, benzyl or phenyl;

[0106] Re is C 2-10 alkenyl;

[0107] M is Ti, Zr or Hf;

[0108] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0109] Each n is 0-3;

[0110] Each R2 is the same or different and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0111] Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10Alkyl or phenyl; and

[0112] Each p is 0-3; for example, a racemic metallocene complex of formula (Ia')

[0113]

[0114] wherein each X is a σ-donating ligand;

[0115] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0116] L is a (RdRe)Si group;

[0117] Rd is C 1-10 alkyl;

[0118] Re is C 2-10 alkenyl;

[0119] M is Ti, Zr or Hf;

[0120] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0121] Each n is 0-3;

[0122] Each R2 is the same or different and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group;

[0123] Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and

[0124] Each p is 0-3.

[0125] The following preferences apply to all formulae herein.

[0126] M is preferably Zr or Hf, more preferably Zr.

[0127] Each X is independently a σ-donating ligand. Thus, each X may be the same or different and is preferably a hydrogen atom, a halogen atom, a linear or branched, cyclic or acyclic C 1-20 -alkyl or C 1-20 -alkoxy, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 -Arylalkyl.

[0128] In one embodiment, the X group can be a trihydrocarbylsilyl group, a C1-10 -alkoxy, C 1-10 Alkoxy-C 1-10 - an alkyl group or an amide group.

[0129] The term "halogen" includes fluorine, chlorine, bromine and iodine, with chlorine being preferred.

[0130] The amide groups of interest are -NH2, -NHC 1-6 Alkyl or -N(C 1-6 Alkyl)2.

[0131] More preferably, each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl.

[0132] More preferably, each X is independently a halogen atom, a linear or branched C 1-4 -alkyl or C 1-4 - alkoxy, phenyl or benzyl.

[0133] Most preferably, each X is independently chloro, benzyl, cyclohexyl or methyl.

[0134] Preferably, the two X groups are identical.

[0135] Most preferably, the two X groups are two chlorides, two methyls or two benzyls, especially two chlorides.

[0136] L is a bridge based on carbon, silicon or germanium. There are one or two main chain connecting atoms between the two ligands, such as the structure of ligand-C-ligand (one main chain atom) or ligand-Si-Si-ligand (two main chain atoms).

[0137] The bridging atom can connect other groups. For example, suitable bridging ligands L are selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C2-atom optionally including one or more heteroatoms of Groups 14-16 of the Periodic Table or fluorine atoms. 20 - a hydrocarbon group, or optionally two R' groups together may form a ring. In one embodiment, R' may be an alkyl group having 1 to 10 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms.

[0138] The term "heteroatom belonging to Groups 14 to 16 of the periodic table" includes Si, N, O or S, for example.

[0139] Preferably, L is -R'2Si-, vinyl or methylene.

[0140] In the formula -R'2Si-, preferably, each R' is independently C1-C 20 -hydrocarbon group. Therefore, the term C 1-20 -Hydrocarbon groups include C 1-20 -alkyl, C 2-20 -Alkenyl, C 2-20 -Alkynyl, C 3-20 -Cycloalkyl, C 3-20 -cycloalkenyl, C 6-20 -Aryl, C 7-20 -alkylaryl or C 7-20 -arylalkyl or of course mixtures of these groups, for example cycloalkyl substituted by alkyl. Unless otherwise specified, preferred C 1-20 -The hydrocarbon group is C 1-20 -alkyl, C 2-20 -Alkenyl, C 4-20 -Cycloalkyl, C 5-20 -cycloalkyl-alkyl, C 7-20 -alkylaryl, C 7-20 -Arylalkyl group or C 6-20 -Aryl.

[0141] In one embodiment, the formula -R'2Si- represents a silacycloalkanediyl group, such as silacyclobutane, silacyclopentane or 9-silafluorene.

[0142] In one embodiment, L is (RdRe)Si, and Rd is C 1-10 Alkyl, C 5-10 -cycloalkyl, benzyl or phenyl, and Re is C 2-10 alkenyl, for example L is (RdRe)Si, and Rd is C 1-4 alkyl, cyclohexyl, benzyl or phenyl, and Re is C 4-8 For the avoidance of doubt, in a (RdRe)Si group, the Rd group and the Re group are bonded to the Si atom.

[0143] In one embodiment, each R' is different. Preferably, one R' is C 1-10 Alkyl groups, such as C 1-4 Alkyl, especially methyl, one R' is C 2-10 Alkenyl, such as C 4-8 Preferably, the double bond is located at the end of the alkenyl group distal to the Si bridge. Most preferably, the bridge is =Si(CH3)(-CH2CH2CH2CH=CH2).

[0144] In another embodiment, the two R' groups are the same. Preferably, R' is C1-C 10-hydrocarbon, or an alkyl group having 1 to 10 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms. Preferred R' groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 2-10 Alkenyl, C 3-8 -cycloalkyl, cyclohexylmethyl, phenyl or benzyl, more preferably, each R' is independently C1-C6-alkyl, C 2-10 Alkenyl, C 5-6 -cycloalkyl or phenyl, most preferably both R' are methyl or one is methyl and the other is cyclohexyl. Most preferably, the bridge is -Si(CH3)2-.

[0145] Het groups may be identical or different, preferably identical. Het groups are monocyclic or polycyclic heteroaromatic or heterocyclic groups comprising at least one heteroatom selected from O, N or S. If N is present in the ring, it may carry an H group or a C 1-6 alkyl.

[0146] Preferably, the Het group is monocyclic. Preferably, the Het group is a heteroaryl group. Preferably, the Het group is a monocyclic heteroaryl group. Preferably, the Het group is a 5- or 6-membered heteroaryl ring or heterocyclic structure.

[0147] Preferred Het groups include furanyl, tetrahydrofuranyl, thienyl, pyridinyl, piperidinyl or pyrrole.

[0148] Preferably, there is one heteroatom in the Het ring. Preferably, the heteroatom is O or S, preferably O. Most preferably, Het is furanyl. Preferably, the connection from the Het group to the cyclopentadienyl ring is on a carbon adjacent to the heteroatom. Preferably, the connection from the Cp group to the Het ring is on a carbon adjacent to the linker L.

[0149] Each R1 is the same or different and is a straight chain C 1-10 Alkyl, or straight chain C 1-10 Alkoxy.

[0150] Preferably, each R1 is a linear C 1-6 Alkyl, or straight chain C 1-6 Alkoxy.

[0151] More preferably, R1 is methyl or ethyl.

[0152] The subscript "n" is preferably 1 or 2, ie preferably the ring is substituted. If n is 2, then preferably R1 is methyl.

[0153] If n is greater than 1, preferably the R1 groups are not bonded to the same C atom.

[0154] If n=2, preferably, the R1 groups are adjacent. If n=2, preferably, the R1 groups are attached to the carbon adjacent to the bridge L and to the next carbon.

[0155] If n=1, preferably, the R1 group is not adjacent to the linker L or Het group.

[0156] Preferably, R2 is a -Si(RaRbRc) group (eg SiR3, wherein the three R groups are Ra, Rb and Rc).

[0157] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; preferably C 1-6 alkyl.

[0158] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; preferably C 1-6 alkyl.

[0159] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl.

[0160] Each p is 0-3 or 1-3, for example, 1-2.

[0161] Preferably, Ra, Rb and Rc groups are phenyl or C 1-4 In one embodiment, one Rc is phenyl and the Ra and Rb groups are C 1-4 In another embodiment, all Ra, Rb and Rc groups are C 1-4 Alkyl groups are preferably -SiPhMe2 or SiMe3.

[0162] Preferably, p is 0 or 1, more preferably p=1.

[0163] If p is not 0, then preferably, the R2 substituent is located on a carbon adjacent to a heteroatom. Preferably, the R2 group is not bonded to the same carbon atom to which the Cp ring is attached. If the Het group is furanyl, then preferably, the Het ring is attached to the Cp ring and the Het group (if present) via two carbon atoms adjacent to O.

[0164] The racemic complex used in the present invention preferably has the formula (II):

[0165]

[0166] Wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C1-6 - alkoxy, amide, phenyl or benzyl. ;

[0167] Each Het is independently a monocyclic or polycyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0168] L is -R'2C- or -R'2Si-, wherein each R' is independently a C substituted by an alkoxy group having 1 to 10 carbon atoms. 1-20 Hydrocarbon or C 1-10 alkyl;

[0169] M is Ti, Zr or Hf;

[0170] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy,

[0171] Each n is 0-3;

[0172] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0173] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl;

[0174] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl;

[0175] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl;

[0176] Each p is 0-3;

[0177] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 Alkyl substituted phenyl and p is 1-3.

[0178] Ideally, in formula (II), R1 is a linear C 1-6 An alkyl group, such as a methyl group.

[0179] The racemic complex used in the present invention preferably has the formula (III):

[0180]

[0181] Wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6-alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0182] Each Het is independently a monocyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0183] L is -R'2C- or -R'2Si-, wherein each R' is independently a C substituted by an alkoxy group having 1 to 10 carbon atoms. 1-20 Hydrocarbon or C 1-10 alkyl;

[0184] M is Ti, Zr or Hf;

[0185] Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy;

[0186] Each n is 0-3;

[0187] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0188] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0189] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0190] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0191] Each p is 0-3;

[0192] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 Alkyl substituted phenyl and p is 1-3.

[0193] Ideally, in formula (III), R1 is a linear C 1-6 An alkyl group, such as a methyl group.

[0194] The racemic complex used in the present invention preferably has the formula (IV):

[0195]

[0196] Wherein each X is independently a hydrogen atom, a halogen atom, a C1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl. ;

[0197] Each Het is independently a monocyclic heteroaryl group comprising at least one heteroatom selected from O, N or S;

[0198] L is -R'2C- or -R'2Si-, wherein each R' is independently a C substituted by an alkoxy group having 1 to 10 carbon atoms. 1-20 Hydrocarbon or C 1-10 alkyl;

[0199] M is Ti, Zr or Hf;

[0200] Each R1 is the same or different and is a straight chain C 1-6 Alkyl, or straight chain C 1-6 Alkoxy;

[0201] Each n is 0-3;

[0202] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0203] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0204] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0205] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0206] Each p is 0-3;

[0207] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 Alkyl substituted phenyl and p is 1-3.

[0208] Ideally, in formula (IV), R1 is a linear C 1-6 An alkyl group, such as a methyl group.

[0209] The racemic complex used in the present invention preferably has the formula (V)

[0210]

[0211] Wherein each X is independently a hydrogen atom, a halogen atom, a C1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0212] Each Het is independently a monocyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O or S;

[0213] L is or -R'2Si-, wherein each R' is independently a C substituted by an alkoxy group having 1 to 10 carbon atoms. 1-20 Hydrocarbon or C 1-10 alkyl;

[0214] M is Ti, Zr or Hf;

[0215] Each R1 is the same or different and is a straight chain C 1-6 Alkyl or straight chain C 1-6 Alkoxy;

[0216] Each n is 1-2;

[0217] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0218] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0219] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0220] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0221] Each p is 0-1;

[0222] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 The phenyl group is alkyl substituted and p is 1.

[0223] Ideally, in formula (V), R1 is a linear C 1-6 An alkyl group, such as a methyl group.

[0224] The racemic complex used in the present invention preferably has the formula (VI):

[0225]

[0226] Wherein each X is independently a hydrogen atom, a halogen atom, a C1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl. ;

[0227] Each Het is independently a monocyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O or S;

[0228] L is -R'2Si-, wherein each R' is independently C 1-10 Alkyl, C 3-8 Cycloalkyl or C 2-10 alkenyl;

[0229] M is Ti, Zr or Hf;

[0230] Each R1 is the same or different and is a straight chain C 1-6 alkyl;

[0231] Each n is 1-2;

[0232] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0233] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0234] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0235] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0236] Each p is 0-1;

[0237] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 The phenyl group is alkyl substituted and p is 1.

[0238] Ideally, in formula (VI), R1 is a linear C 1-6 An alkyl group, such as a methyl group.

[0239] The racemic complex used in the present invention preferably has the formula (VII):

[0240]

[0241] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6-alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0242] L is a divalent bridge based on carbon, silicon or germanium, in which one or two backbone atoms are linked to the ligand, such as -R'2Si-, where each R' is independently C 1-20 A hydrocarbon group or a C substituted alkoxy group having 1 to 10 carbon atoms 1-10 alkyl;

[0243] Each R1 is the same or different and is a straight chain C 1-6 Alkyl groups, such as methyl;

[0244] Each n is 0-3;

[0245] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0246] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0247] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0248] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0249] Each p is 0-1;

[0250] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 The phenyl group is alkyl substituted and p is 1.

[0251] The racemic complex used in the present invention preferably has the formula (VIII):

[0252]

[0253] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0254] L is a divalent bridge based on carbon, silicon or germanium, in which one or two backbone atoms are linked to the ligand, such as -R'2Si-, where each R' is independently C 1-20A hydrocarbon group or a C substituted alkoxy group having 1 to 10 carbon atoms 1-10 alkyl;

[0255] Each R1 is the same or different and is a straight chain C 1-6 Alkyl groups, such as methyl;

[0256] Each n is 1-2;

[0257] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0258] Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0259] Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0260] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-6 Alkyl or phenyl;

[0261] Each p is 0-1;

[0262] Where L is not a (RdRe)Si group; Where Rd is C 1-10 Alkyl and Re is C 2-10 alkenyl, then Rc is optionally substituted by 1-3 C 1-6 The phenyl group is alkyl substituted and p is 1.

[0263] The racemic complex used in the present invention preferably has the formula (IX):

[0264]

[0265] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0266] L is Me2Si- or (Me)C 2-10 -Alkenyl Si;

[0267] Each R1 is the same or different and is a straight chain C 1-6 Alkyl groups, such as methyl;

[0268] Each n is 1-2;

[0269] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0270] Ra is C 1-6 Alkyl or phenyl;

[0271] Rb is C 1-6 Alkyl or phenyl;

[0272] Rc is C 1-6 Alkyl or phenyl;

[0273] Each p is 1;

[0274] If L is not (Me)C 2-10 -alkenyl Si, then Rc is phenyl;

[0275] For example, formula (IX')

[0276]

[0277] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0278] L is Me2Si- or (Me)C 2-10 -Alkenyl Si;

[0279] Each R1 is the same or different and is a straight chain C 1-6 Alkyl groups, such as methyl;

[0280] Each n is 1-2;

[0281] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0282] Ra is C 1-6 Alkyl or phenyl;

[0283] Rb is C 1-6 Alkyl or phenyl;

[0284] Rc is C 1-6 Alkyl or phenyl;

[0285] Wherein if L is (Me)2Si, then Rc is phenyl;

[0286] The preferred novel complex is the racemic complex of formula (X)

[0287]

[0288] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0289] L is a divalent bridge based on carbon, silicon or germanium, in which one or two backbone atoms are linked to the ligand, such as -R'2Si-, where each R' is independently C 1-20 A hydrocarbon group or a C substituted alkoxy group having 1 to 10 carbon atoms 1-10 alkyl;

[0290] M is Ti, Zr or Hf;

[0291] Each Het is independently a monocyclic heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S;

[0292] Each R1 is the same or different and is a straight chain C 1-10 Alkyl groups, such as methyl;

[0293] Each n is 1-3;

[0294] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0295] Ra is C 1-6 alkyl;

[0296] Rb is C 1-6 alkyl;

[0297] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted phenyl;

[0298] Each p is 1-3; for example, the formula (X')

[0299]

[0300] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0301] L is a divalent bridge based on carbon, silicon or germanium, in which one or two backbone atoms are linked to the ligand, such as -R'2Si-, where each R' is independently C 1-20 A hydrocarbon group or a C substituted group having 1 to 10 carbon atoms 1-10 alkyl;

[0302] Each R1 is the same or different and is a straight chain C 1-10 Alkyl groups, such as methyl;

[0303] Each n is 1-3;

[0304] Each R2 is the same or different and is a -Si(RaRbRc) group;

[0305] Ra is C 1-6 alkyl;

[0306] Rb is C 1-6 alkyl;

[0307] Rc is optionally replaced by 1-3 C 1-6 Alkyl substituted phenyl.

[0308] Ideally, in formula (X or X'), R1 is a linear C 1-6 alkyl.

[0309] Even more preferred novel complexes are those of formula (XII)

[0310]

[0311] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl;

[0312] Each Het is independently a monocyclic heteroaryl group comprising at least one heteroatom selected from O, N or S;

[0313] L is a (RdRe)Si group;

[0314] Rd is C 1-10 alkyl;

[0315] Re is C 2-10 alkenyl;

[0316] M is Ti, Zr or Hf;

[0317] Each R1 is the same or different and is a straight chain C 1-10 Alkyl groups, such as methyl;

[0318] Each n is 1-3;

[0319] Each R2 is the same or different and is a -Si(R)3 group;

[0320] Each R is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and

[0321] Each p is 0-3; for example, in formula (XII')

[0322]

[0323] wherein each X is a sigma donor ligand, for example wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C1-6 - alkoxy, amide, phenyl or benzyl;

[0324] L is a (RdRe)Si group;

[0325] Rd is C 1-10 alkyl;

[0326] Re is C 2-10 alkenyl;

[0327] Each R1 is the same or different and is a straight chain C 1-10 Alkyl groups, such as methyl;

[0328] Each n is 1-3;

[0329] Each R2 is the same or different and is a -Si(R)3 group;

[0330] Each R is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl.

[0331] Ideally, in formula (XII or XII'), R1 is a linear C 1-6 An alkyl group, such as a methyl group.

[0332] Highly preferred complexes are

[0333]

[0334]

[0335] The metallocenes of the present invention can be prepared using known synthetic chemistry methods similar to those outlined in US Pat. No. 6,326,493 and in the Examples section below.

[0336] Catalyst

[0337] In order to form an active catalytic species, it is usually necessary to use a promoter which is well known in the art.

[0338] According to the present invention, a cocatalyst comprising a Group 13 element is required, such as a cocatalyst comprising boron or a cocatalyst comprising Al. Most preferably, an aluminoxane cocatalyst is used in combination with the metallocene catalyst complex defined above.

[0339] The aluminoxane cocatalyst may be one of formula (A):

[0340]

[0341] wherein n is 6-20 and R has the following meanings.

[0342] Aluminoxanes are formed upon partial hydrolysis of organoaluminum compounds, such as compounds of the formula AlR3, AlR2Y, and Al2R3Y3, wherein R can be, for example, C1-C 10 -alkyl, preferably C1-C5-alkyl, or C3-C 10 -cycloalkyl, C7-C 12 -arylalkyl or -alkylaryl and / or phenyl or naphthyl, wherein Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C 10 - an alkoxy group, preferably a methoxy group or an ethoxy group. The oxygen-containing aluminoxane obtained is usually not a pure compound but a mixture of oligomers of the formula (A).

[0343] The preferred aluminoxane is methylaluminoxane (MAO). According to the present invention, since the aluminoxane used as a cocatalyst is not a pure compound due to the way it is prepared, the molar concentration of the aluminoxane solution hereinafter is based on its aluminum content.

[0344] Boron-containing cocatalysts may also be used, optionally in combination with aluminoxane cocatalysts. Boron-containing cocatalysts of interest include those of formula (B):

[0345] BY3

[0346] (B)

[0347] Wherein Y is identical or different and is a hydrogen atom, an alkyl group of 1 to about 20 carbon atoms, an aryl group of 6 to about 15 carbon atoms, an alkylaryl group, an aralkyl group, a haloalkyl group or a haloaryl group, each of which has 1 to 10 carbon atoms in the alkyl group and 6-20 carbon atoms in the aryl group, or fluorine, chlorine, bromine or iodine. Preferred embodiments of Y are fluorine, trifluoromethyl, aromatic fluorinated groups, such as p-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-bis(trifluoromethyl)phenyl. Preferred are trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and / or tris(3,4,5-trifluorophenyl)borane.

[0348] Tris(pentafluorophenyl)borane is particularly preferred.

[0349] However, preference is given to using borates, ie compounds comprising borate.

[0350] These compounds generally contain anions of formula (C):

[0351] (Z)4B -

[0352] (C)

[0353] wherein Z is an optionally substituted phenyl derivative, the substituent being a halo-C 1-6 - alkyl or halogen group. Preferably it is fluorine or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.

[0354] Such ionic promoters preferably comprise a weakly coordinating anion, such as tetrakis(pentafluorophenyl)borate or tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0355] Suitable cationic counterions include triphenylcarbonium and are protonated amine or aniline derivatives, such as methylammonium, aniline, dimethylammonium, diethylammonium, N-methylaniline, diphenylammonium, N,N-dimethylaniline, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridine, p-bromo-N,N-dimethylaniline or p-nitro-N,N-dimethylaniline.

[0356] Preferred ionic compounds that can be used according to the present invention include:

[0357] Tributylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(trifluoromethylphenyl)borate, tributylammonium tetrakis(4-fluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate, NN-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammonium tetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate or ferrocenium tetrakis(pentafluorophenyl)borate.

[0358] Preferred are triphenylcarbonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate or N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

[0359] Therefore, preferred borates for use in the present invention contain a trityl group, ie, a triphenylcarbonium ion. Therefore, the use of Ph3CB(PhF5)4 and the like is particularly preferred.

[0360] Suitable amounts of promoter are well known to those skilled in the art.

[0361] Preferably, the amount of cocatalyst is selected so as to achieve a molar ratio below the defined value.

[0362] The molar ratio of boron (B) feed to the metal ion (M) of the metallocene (preferably zirconium) may be in the range of 0.1:1 to 10:1 mol / mol, preferably 0.3:1 to 7:1, especially 0.3:1 to 5:1 mol / mol.

[0363] Even more preferably, the molar ratio of the feed amount of boron (B) to the metal ion (M) of the metallocene (preferably zirconium) is between 0.3:1 and 3:1.

[0364] The molar ratio Al / M of Al of the aluminoxane to the metal ion (M) of the metallocene (preferably zirconium) may be in the range of 1:1 to 2000:1 mol / mol, preferably 10:1 to 1000:1, more preferably 50:1 to 600:1 mol / mol.

[0365] Catalyst system

[0366] The metallocene complexes as described above are used in combination with a suitable cocatalyst combination as described above.

[0367] The catalyst system of the present invention can be used in solid but unsupported form according to the scheme in WO03 / 051934. The catalyst system of the present invention is preferably used in solid supported form. The particulate support material used is preferably an inorganic porous support, such as silicon dioxide, aluminum oxide or a mixed oxide such as silicon dioxide-alumina, in particular silicon dioxide.

[0368] Preference is given to using a silica support.

[0369] Particularly preferably, the support is a porous material so that the complex can be loaded into the pores of the particulate support, for example using methods similar to those described in WO94 / 14856, WO95 / 12622, WO2006 / 097497 and EP1828266.

[0370] The average particle size of the support, such as a silica support, may generally be 10 to 100 μm.

[0371] The average pore size of a support such as a silica support may be in the range of 10-100 nm and the pore volume 1-3 mL / g.

[0372] Examples of suitable support materials are, for example, ES757 produced and sold by PQ Corporation, Sylopol 948 produced and sold by Grace or SUNSPERA DM-L-303 silica produced by AGC Si-Tech Co. The support may optionally be calcined before use in catalyst preparation to achieve an optimum silanol group content.

[0373] The catalyst may comprise 5-500 μmol, for example 10-100 μmol, of transition metal per gram of support, for example silica, and 3-15 mmol of Al per gram of support, for example silica.

[0374] One-step preparation of catalyst

[0375] In order to prepare the catalyst used in the present invention, it is necessary to combine the metallocene complex, the cocatalyst and the support. In a preferred embodiment, the process of combining all of these components occurs in a single step.

[0376] Thus, preferably, a solution in which the metallocene complex and the cocatalyst are combined in a solvent is prepared, usually under an inert atmosphere. Preferred solvents are hydrocarbons, such as toluene and xylene.

[0377] The resulting solution is then added, preferably rapidly, to a support, such as a silica support. The resulting crude catalyst is then gently mixed and allowed to stand before drying. A washing step may be used if desired.

[0378] The solution of metallocene complex and cocatalyst is preferably added dropwise to the support, ideally over a short period of time, such as less than 10 minutes.

[0379] The total volume of solution that can be impregnated is preferably less than to slightly above the pore volume specification of the support so that impregnation is achieved in a "dry mix" / "pore fill" / "incipient wetness" mode.

[0380] Ideally, the contacting step occurs at a temperature of 10-30° C. This step is typically exothermic.

[0381] Therefore, from one aspect, the present invention provides a method for preparing a metallocene catalyst, comprising:

[0382] (I) contacting a solid support with a cocatalyst solution comprising a compound of a Group 13 element and a racemic metallocene complex as defined above to form a supported catalyst.

[0383] When using this one-step process to prepare supported catalysts, we found that some surprising technical effects were observed.

[0384] - The preferred furanyl substituted metallocenes have higher catalyst activity in slurry phase compared to other metallocene catalysts, such as those based on bis(1-methyl-3-n-butylcyclopentadienyl)zirconium chloride.

[0385] Higher comonomer response

[0386] High molecular weight capability

[0387] Adjustment of MFR with hydrogen without significant loss of catalyst activity

[0388] Excellent polymer particle morphology (good polymer bulk density)

[0389] Significantly reduces polymer density

[0390] Stable kinetic curve, suitable for multi-stage process

[0391] Reduce long-chain polymer branching.

[0392] The key here is the comonomer sensitivity, M w Capacity and good activity combined with a higher gas phase to slurry phase activity ratio.

[0393] Two-step catalyst preparation

[0394] In a second embodiment, the contact between the support, the metallocene complex and the cocatalyst occurs in a stepwise manner. In the first step, the support, such as a silica support, is contacted with the cocatalyst. Therefore, a solution of the cocatalyst in a solvent is generally contacted with the support. The solvent of interest is also a hydrocarbon solvent, such as toluene and xylene. Ideally, the temperature for carrying out the contacting step is room temperature or lower, such as -10 to 25°C. The contacting step can be carried out under an inert atmosphere.

[0395] Once the promoter has been allowed to impregnate the support (e.g. after stirring the mixture for a period of time), the system is preferably heated to at least 70° C. while the impregnation process continues, e.g. 70 to 120° C. The system is then allowed to settle (preferably still at elevated temperature) and the supernatant liquid removed.

[0396] The impregnated support may then be washed with more solvent, ideally once more at an elevated temperature, and then the solvent removed. The washing steps may be repeated, perhaps each at a lower temperature than the previous step, and then dried.

[0397] The impregnated support thus produced, for example in dry form, is then contacted with the metallocene complex. This may conveniently be provided as a solution, ideally in the same solvent as that used to make the impregnated support. The metallocene complex is allowed to impregnate the support before the solvent is removed to leave the dry supported catalyst. A washing step may again be employed. The second step may be carried out at a temperature of 20-60°C.

[0398] Therefore, from one aspect, the present invention provides a method for preparing a metallocene catalyst, comprising:

[0399] (I) contacting a solid support with a promoter solution comprising a compound of a Group 13 element; thereby forming a support impregnated with the promoter;

[0400] (II) contacting the support impregnated with the promoter with a racemic metallocene complex as defined above;

[0401] Thus, a supported catalyst is formed.

[0402] Olefin polymers

[0403] The present invention also relates to the preparation of olefin polymers, such as polyethylene or polypropylene polymers, using the catalyst of the present invention. In particular, the olefin polymer is a polyethylene polymer, such as a unimodal or multimodal polyethylene homopolymer or copolymer using the catalyst of the present invention.

[0404] The density of ethylene homopolymer or copolymer can be between 900 and 980 kg / m 3 between.

[0405] Preferably, the polyethylene polymer is a copolymer. More preferably, the polyethylene copolymer is LLDPE. Its density may be 905 to 940 kg / m 3 , preferably 910 to 935 kg / m 3 , more preferably 915 to 930 kg / m 3 , especially 916 to 928 kg / m 3 In one embodiment, preferably 910 to 928 kg / m 3 The term "LLDPE" herein refers to linear low density polyethylene.

[0406] The LLDPE is preferably multimodal. The term "multimodal" includes polymers which are multimodal with respect to the MFR, thus also bimodal polymers. The term "multimodal" may also refer to multimodality with respect to the "comonomer distribution".

[0407] Often, polymers comprising at least two polyethylene fractions, which have been produced under different polymerisation conditions, resulting in different (weight average) molecular weights and molecular weight distributions of the fractions, are referred to as "multimodal". The prefix "multi" relates to the number of different polymer fractions present in the polymer. Thus, for example, the term "multimodal polymer" includes so-called "bimodal" polymers consisting of two fractions. The form of the molecular weight distribution curve, i.e. the appearance of a plot of the polymer weight fraction as a function of its molecular weight for a multimodal polymer, such as LLDPE, may show two or more maxima, or at least be significantly broadened compared to the curves for the individual fractions. Typically, the resulting MWD curve will be broad, sloping or show a shoulder.

[0408] Ideally, the molecular weight distribution curve of the multimodal polymer produced using the metallocene catalyst of the present invention will show two different maxima. Alternatively, the polymer components have similar MFR and are bimodal in comonomer content. A polymer comprising at least two polyethylene components, which have been produced under different polymerization conditions, resulting in different comonomer contents of the components, is also referred to as "multimodal".

[0409] For example, if a polymer is produced in a sequential multi-stage process, utilizing a series of reactors connected in series and using different conditions in each reactor, the polymer components produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight. When a molecular weight distribution curve for such a polymer is recorded, the individual curves from these components are superimposed into the molecular weight distribution curve for the resulting total polymer product, typically resulting in a curve with two or more distinct maxima.

[0410] In any multimodal polymer, there may be a lower molecular weight component (LMW) and a higher molecular weight component (HMW). The molecular weight of the LMW component is lower than that of the higher molecular weight component. The difference is preferably at least 5000 g / mol.

[0411] The unimodal or multimodal polyethylene polymer produced according to the present invention preferably comprises at least one C4-10-comonomer. The comonomer may be present in the HMW component (or second component) or in the LMW component (or first component) or in both. From here on, the term "MW / HMW component" will be used, but the described embodiments apply to the first component and the second component separately.

[0412] Preferably, the HMW component comprises at least one C4-10 comonomer. The LMW component may then be an ethylene homopolymer or may also comprise at least one C4-10 comonomer. In one embodiment, the multimodal polyethylene polymer comprises a single comonomer. In a preferred embodiment, the multimodal polyethylene polymer comprises at least two, such as exactly two, C4-10 comonomers.

[0413] In one embodiment, the multimodal polyethylene polymer is a terpolymer and includes at least two C4-10 comonomers. In that case, the HMW component may be a copolymer component or a terpolymer component and the lower molecular weight (LMW) component may be an ethylene homopolymer component or a copolymer component. Alternatively, both the LMW and HMW components may be copolymers such that at least two C4-10 comonomers are present.

[0414] Thus, a multimodal polyethylene polymer may be a polymer wherein the HMW component comprises poly(ethylene) derived from ethylene and at least two other C 4-10 Repeating units of alpha olefin monomers, such as 1-butene and a C 6-10 Alpha olefin monomers. Ethylene preferably constitutes the majority of the LMW or HMW component. In a most preferred embodiment, the LMW component may include ethylene-1-butene copolymer and the HMW component may include ethylene-1-hexene copolymer.

[0415] The total comonomer content in the ethylene polymer may be, for example, 0.5-8.0%, preferably 0.7-6.5%, more preferably 1.0-5.0% and most preferably 1.5-5.0% on a mole basis.

[0416] 1-Butene may be present in an amount of 0.2 to 2.5% by mole, such as 0.4-2%, more preferably 0.4-1.5% and most preferably 0.4-1%.

[0417] The C6-C10 alpha olefin may be present in an amount of 0.3-5.5%, preferably 0.4-4.5%, more preferably 0.7-4.5%, on a mole basis.

[0418] Preferably, the LMW component has a lower amount (mol%) of comonomer than the HMW component, for example the amount of comonomer preferably 1-butene in the LMW component is 0.05-0.9 mol%, more preferably 0.1-0.8 mol%, while the amount of comonomer preferably 1-hexene in the HMW component (B) is 1.0-8.0 mol%, more preferably 1.2 to 7.5 mol%.

[0419] If desired, comonomer content in HMW component (mol%) = (comonomer content in final product (mol%) - (weight fraction of LMW component *comonomer content in LMW component (mol%))) / (weight fraction of HMW component).

[0420] Thus a multimodal polyethylene copolymer may be formed from ethylene together with at least one of 1-butene, 1-hexene or 1-octene. The multimodal polyethylene polymer may be an ethylene butene hexene terpolymer, for example wherein the HMW component is an ethylene butene hexene terpolymer and the LMW is an ethylene homopolymer component. It is also envisaged to use a terpolymer of ethylene with 1-butene and 1-octene comonomers, or a terpolymer of ethylene with 1-octene and 1-hexene comonomers.

[0421] In a further embodiment, the multimodal polyethylene copolymer may comprise two ethylene copolymers, such as two ethylene butene copolymers or an ethylene butene copolymer (e.g. as a LMW component) and an ethylene hexene copolymer (e.g. as a HMW component). It is also possible to combine an ethylene copolymer component and an ethylene terpolymer component, such as an ethylene butene copolymer (e.g. as a LMW component) and an ethylene butene hexene terpolymer (e.g. as a HMW component).

[0422] The LMW component of the multimodal polyethylene polymer may have an MFR2 of 0.5-3000 g / 10min, more preferably 1.0-1000 g / 10min. In some embodiments, the MFR2 of the LMW component may be 50 to 3000 g / 10min, more preferably 100 to 1000 g / 10min, e.g. targeting cast films. In some embodiments, the MFR2 of the LMW component may be 0.5-50 g / 10min, more preferably 1.0-10 g / 10min, preferably 1.5-9.0 and more preferably 2.0-8.5, e.g. targeting blown films.

[0423] The molecular weight of the low molecular weight component should preferably be in the range of 20,000-90,000, such as 60,000-90,000.

[0424] It may have a minimum of 925 kg / m 3 Density, for example at least 940 kg / m 3 The density can range from 930-950, preferably 935 to 945 kg / m 3 .

[0425] The HMW component of the multimodal polyethylene polymer may for example have an MFR2 of less than 1 g / 10 min, for example 0.2-0.9 g / 10 min, preferably 0.3-0.8 and more preferably 0.4-0.7 g / 10 min. It may have a density of less than 915 kg / m 3 , for example, less than 910kg / m 3 , preferably less than 905kg / m 3 The Mw of the higher molecular weight component may preferably be in the range of 100,000 to 1,000,000, for example 250,000 to 500,000.

[0426] The LMW component may constitute 30-70 wt%, such as 40-60 wt%, in particular 45-55 wt% of the multimodal polyethylene polymer.

[0427] The HMW component may constitute 30-70 wt%, such as 40-60 wt%, in particular 45-55 wt% of the multimodal polyethylene polymer.

[0428] In one embodiment, the LMW component is 40-45 wt% and the HMW component is 60-55 wt%.

[0429] In one embodiment, the polyethylene polymer consists of HMW and LMW components as the only polymer components.

[0430] The MFR2 of the multimodal polyethylene polymer may be 0.01-50 g / 10 min, preferably 0.05-25 g / 10 min, especially 0.1-10 g / 10 min.

[0431] The density of the multimodal polyethylene polymer may be 900-960 kg / m 3 , preferably 905-940kg / m 3 , especially 910-935kg / m 3 .

[0432] Molecular weight distribution (MWD, M w / M n ) is in the range of 2.0-15.0, preferably in the range of 2.2-10.0, and more preferably in the range of 2.4-4.6.

[0433] Multimodal (e.g. bimodal) polyethylene polymers are produced by in situ blending in a multistage polymerization process. Specifically, the process requires

[0434] (I) polymerizing ethylene and optionally at least one C4-10 alpha olefin comonomer in a first stage in the presence of a metallocene catalyst to form a first polyethylene component; and

[0435] (II) polymerizing ethylene and optionally at least one C4-10 alpha olefin comonomer in a second stage in the presence of the product of step (I) to form a second component.

[0436] The olefin polymers may be produced in any suitable polymerization process known in the art, wherein the polymerization is typically carried out in solution, slurry, bulk or gas phase. Preferably, the multimodal polymer is produced in at least two stages of polymerization, using for example two slurry reactors or two gas phase reactors or any combination thereof, in any order used. Preferably, however, slurry polymerization is used to prepare the multimodal polymer, for example in a loop reactor, followed by gas phase polymerization in a gas phase reactor.

[0437] The loop reactor - gas phase reactor system is marketed by Borealis as the BORSTAR reactor system.Thus, any multimodal polyethylene polymer present is preferably formed in a two stage process comprising a first slurry loop polymerisation followed by a gas phase polymerisation.

[0438] The conditions used in this process are well known. For slurry reactors, the reaction temperature is usually in the range of 60-110° C. (e.g. 85-110° C.), the reactor pressure is usually in the range of 5-80 bar (e.g. 50-65 bar), and the residence time is usually in the range of 0.3-5 hours (e.g. 0.5-2 hours). The diluent used is usually an aliphatic hydrocarbon with a boiling point in the range of -70 to +100° C., such as propane. In such reactors, if desired, the polymerization can be carried out under supercritical conditions. It is also possible to carry out slurry bulk polymerization, in which the reaction medium is formed by the monomers being polymerized.

[0439] The ethylene content of the liquid phase of the slurry may be from 2 to about 50%, preferably from about 2 to about 20%, and especially from about 3 to about 12%, on a molar basis.

[0440] As is known in the art, hydrogen may be fed into the reactor to control the molecular weight of the polymer.

[0441] For gas phase reactors, the reaction temperature used is usually in the range of 60-115° C. (e.g., 70-110° C.), the reactor pressure is usually in the range of 10-25 bar, and the residence time is usually 1-8 hours. The gas used is usually a non-reactive gas, such as nitrogen or a low boiling hydrocarbon, such as propane and a monomer (e.g., ethylene).

[0442] Preferably, the lower molecular weight polymer component is produced in a continuously operated loop reactor in which ethylene and any comonomers are polymerized in the presence of a polymerization catalyst as described above and a chain transfer agent such as hydrogen. The diluent is typically an inert aliphatic hydrocarbon, preferably isobutane or propane.

[0443] The same catalyst can then be used in a gas phase reactor to form higher molecular weight components.

[0444] Further polymerisation steps may also be used, for example further gas phase steps.

[0445] It is generally preferred to remove the reactants of the previous polymerization stage from the polymer before introducing the polymer into the subsequent polymerization stage. It is preferred to do this when transferring the polymer from one polymerization stage to another.

[0446] The catalyst may be transferred to the first reactor by any means known in the art. For example, the catalyst may be suspended in a diluent and maintained as a slurry, the catalyst may be mixed with a viscous mixture of grease and oil and the resulting paste may be fed to the polymerization zone, or the catalyst may be allowed to settle and a portion of the catalyst sludge thus obtained may be introduced into the polymerization reaction.

[0447] If the higher molecular weight component is secondary in a multistage polymerization, its properties cannot be measured directly. However, one skilled in the art can use equation( The Polymer Processing Society, Europe / Africa Region Meeting, Gothenburg, Sweden, August 19-21, 1997) determines the density, MFR2, etc. of the higher molecular weight component:

[0448]

[0449] According to the Equation, in said equation (eq.3), for MFR2, a=5.2 and b=0.7. In addition, w is the weight fraction of other ethylene polymer components with higher MFR, such as component (A). Thus, the LMW component can be component 1 and the HMW component can be component 2. MIb is the MFR2 of the final polyethylene.

[0450] The method may further comprise a prepolymerization step. The prepolymerization step is a conventional step conventionally used in polymer synthesis.

[0451] The prepolymerization step can be carried out in slurry or in gas phase. Preferably, the prepolymerization is carried out in slurry, preferably in a loop reactor. The prepolymerization is then preferably carried out in an inert diluent, preferably a low boiling hydrocarbon having 1 to 4 carbon atoms or a mixture of these hydrocarbons. The temperature in the prepolymerization step is generally 0 to 90° C., preferably 20 to 80° C. and more preferably 25 to 70° C.

[0452] The pressure is not critical and is generally 1-150 bar, preferably 10-100 bar.

[0453] Preferably the catalyst is introduced entirely into the prepolymerisation step. Preferably the reaction product of the prepolymerisation step is then introduced into the first reactor.

[0454] If present, the prepolymer component is considered to be part of the LMW component.

[0455] Generally, the amount of catalyst used depends on the nature of the catalyst, the reactor type and conditions, and the desired properties of the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of the polymer in any reactor.

[0456] The polymers prepared in the process of the present invention can be used in a variety of applications, such as films, for example blown films or cast films. They can also be used in molding applications.

[0457] The catalyst system prepared according to the present invention has excellent catalytic activity in the entire multi-stage polymerization process and can provide a high weight average molecular weight M wand polymers with high comonomer content.

[0458] The invention will now be defined with reference to the following non-limiting examples and accompanying figures.

[0459] Figure 1 The catalyst activities of IC1, IC2, CC1, CC2, CC3 and CC4 in ethylene slurry copolymerization are shown (Examples IE1-1, IE2-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0460] Figure 2 The catalyst activities of IC1, IC2, CC1, CC2, CC3 and CC4 incorporating 1-hexene in ethylene slurry copolymerization are shown (Examples IE1-1, IE2-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0461] Figure 3 The polymer MFR2 of IC1, IC2, CC1, CC2, CC3 and CC4 in ethylene slurry copolymerization is shown (Examples IE1-1, IE2-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0462] Figure 4 The relationship between the catalyst activity of IC1, IC2, CC1, CC2, CC3 and CC4 and the polymer MFR2 in ethylene slurry copolymerization is shown (Examples IE1-1, IE2-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0463] Figure 5 The relationship between the catalyst activity of IC1, IC2, CC1, CC2, CC3 and CC4 in ethylene slurry copolymerization and the 1-hexene content of the polymer is shown (Examples IE1-1, IE2-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0464] Figure 6 Catalyst kinetic curves for IC1, IC2, CC1, CC2, CC3 and CC4 in ethylene slurry copolymerization (ethylene) are shown (Examples IE1-1, IE2-1, CE1-1, CE2-1, CE3-1 and CE4-1).

[0465] Figure 7 The catalyst activities of IC1, IC2, CC1, CC3 and CC4 in bulk homopolymerization of propylene are shown (Examples IE1-2, IE2-2, CE1-2, CE3-2 and CE4-2).

[0466] Figure 8The relationship between the catalyst activity of IC1, IC2, CC1, CC3 and CC4 and polymer Mw in bulk propylene homopolymerization (Examples IE1-2, IE2-2, CE1-2, CE3-2 and CE4-2) is shown.

[0467] Fig. 9 The polymer mmmm pentad isotacticity of IC1, IC2, CC1, CC3 and CC4 in propylene bulk homopolymerization is shown (Examples IE1-2, IE2-2, CE1-2, CE3-2 and CE4-2).

[0468] Fig.10 The polymer soluble fractions of IC1, IC2, CC1, CC3 and CC4 in propylene bulk homopolymerization are shown (Examples IE1-2, IE2-2, CE1-2, CE3-2 and CE4-2).

[0469] experiment

[0470] Analytical methods

[0471] Catalyst Analysis and Characterization

[0472] Determination of Al and Zr contents in solid catalysts by ICP-OES

[0473] In a glove box, an analytical balance was used to weigh a portion of the catalyst (approximately 40 mg) into a glass weighing boat. The sample was then placed in a steel secondary container equipped with an air inlet and exposed to air overnight. The contents of the weighing boat were then rinsed into an Xpress microwave container (20 mL) using 5 mL of concentrated (65%) nitric acid. The sample was then subjected to microwave-assisted acid digestion using a MARS 6 laboratory microwave apparatus, heating to 150°C over 20 minutes and maintained at 150°C for 35 minutes. The digested sample was cooled to room temperature and then transferred to a 100 mL plastic volumetric flask. A standard solution containing 1000 mg / L yttrium (0.4 mL) was added. The flask was then filled with distilled water and shaken. The solution was filtered through a 0.45 μm nylon syringe filter and analyzed using a Thermo iCAP 6300ICP-OES and iTEVA software.

[0474] The instrument was calibrated using a blank solution (5% HNO3 solution prepared from concentrated nitric acid) and six standard solutions containing 0.005 mg / L, 0.01 mg / L, 0.1 mg / L, 1 mg / L, 10 mg / L and 100 mg / L of Al and Zr. The solutions contained 5% HNO3 (prepared from concentrated nitric acid), 4 mg / L of Y standard in distilled water. Plastic volumetric flasks were used. Curve fitting and 1 / concentration weighting were used for calibration curves. Immediately prior to analysis, blank solutions and 10 mg / L Al and Zr standard solutions containing 4 mg / LY and 5% HNO3 prepared from concentrated nitric acid in distilled water were used to verify and adjust the calibration process (instrument re-adjust slope function). Quality control samples (QC: 1 mg / L Al in distilled water; 2 mg / L Zr and 4 mg / LY and 5% HNO3 solution prepared from concentrated nitric acid) were run to confirm the re-adjust slope. Similarly, QC samples were also run at the end of the planned analysis set.

[0475] The 339.198 nm line was used to monitor the Zr content. The 394.401 nm line was used to monitor the Al content. Y 371.030 nm was used as an internal standard. The reported values ​​were calculated back to the original catalyst sample using the original mass of the catalyst aliquot and the dilution volume.

[0476] Analysis of volatile content in solid catalysts by GC-MS

[0477] Under an inert atmosphere, a test portion of 50-80 mg of catalyst powder was accurately weighed into a 20 mL headspace vial. The vial was capped with an aluminum cap with a PTFE / silicone septum. 1 mL of internal standard solution (50 mg toluene-d8 and 50 mg n-nonane dissolved in 100 mL n-dodecane) was added to the sample vial using a precision microsyringe through the septum cap. The same ISTD solution was used for sample and calibration standard solutions.

[0478] For calibration, standard stock solutions were prepared by accurately weighing 40 mg of each analyte component (n-pentane, n-heptane, and toluene) into a 20 mL volumetric flask and filling to the mark with ISTD solution. Calibration solutions with different analyte concentrations were accurately added to 20 mL headspace vials with six increasing analyte standard stock solutions (0.1-1 mL) and then the internal standard solution was added in decreasing volumes to a total volume of 1.0 mL of ISTD solution in each vial. The analyte content in the final calibration sample ranged from 0.2 mg / mL to 2 mg / mL. For the blank solution, 1 mL of ISTD solution was transferred to a 20 mL headspace vial.

[0479] The measurements were performed using an Agilent 7890B gas chromatograph equipped with an Agilent 7697A headspace sampler and an Agilent 5977A mass spectrometer detector. The carrier gas was 99.9996% helium. The headspace sampler oven temperature was set to 80°C, and the loop and transfer line temperatures were set to 120°C. The vial equilibration time was 15 minutes. For sampling, the headspace vials were filled in a fluid-to-pressure mode and pressurized to 172 kPa at a flow rate of 20 mL / min. The sampling of the loop was increased at a rate of 138 kPa / min, and the final pressure was 34 kPa. The carrier gas flow rate in the DB-ProSteel transfer line with a diameter of 0.53 mm was 54 mL / min.

[0480] The GC inlet was operated in split mode. The inlet temperature was set to 280 °C, the pressure was set to 18.236 psi, the total flow was 111.9 mL / min, the septum purge flow was 3 mL / min, and the split flow was 108 mL / min. The split ratio was 120:1. The inlet liner used an ultra-inert split liner with glass wool.

[0481] Separation was achieved using a ZB-XLB-HT Inferno 60m x 250μm x 0.25μm column (Phenomenex) with a pre-column limiting capillary 3m x 250μm x 0μm. The carrier gas flow rate in the analytical column was 1.1mL / min. The initial oven temperature was 40°C with a hold time of 0.1 minutes. The oven ramp step consisted of a first stage at 5°C / min to 60°C, a second stage at 10°C / min to 120°C, and a third stage at 40°C / min to 250°C.

[0482] The MS detector transfer line was maintained at 300 °C. The MSD was operated in electron impact mode at 70 eV and in scan mode in the range of 33–175 m / z with a step size of 0.1 m / z. The ion source temperature was 230 °C and the quadrupole temperature was set to 150 °C. The threshold was set to 50 counts and the electron multiplier gain factor was set to 1. The detector was turned off after 11.40 min.

[0483] Signal characteristics were determined by retention time (pentane 4.5, heptane 6.3, toluene 7.8, toluene-d8 7.7, and n-nonane 10.0) and target ion m / z (pentane 55.0, heptane 100.0, toluene 91.0, toluene-d8 98.0, and n-nonane 98.0). In addition, qualifier ions were used to confirm the identification (heptane, toluene). The target ion signal for each analyte and internal standard was integrated and compared to the calibration curve, which was established at the beginning of each run using six calibration samples. The calibration curve for the response ratio was linear; sample concentration weighting was applied to pentane. Quality control samples were used in each run to verify the normalization. The mass of the test portion was used to calculate the analyte concentration in two replicates in the sample, and the results were reported as the average.

[0484] Polymer Analysis and Characterization

[0485] Polymer melt flow rate (MFR)

[0486] Melt flow rate (MFR) is determined according to ISO 1133 and is expressed in g / 10 min. MFR is an indicator of the viscosity of the polymer melt. MFR of PE is determined at 190°C and MFR of PP is determined at 230°C. The load under which the melt flow rate is determined is usually indicated by a subscript, e.g. MFR2 is measured under a load of 2.16 kg, MFR 21 It is measured under a load of 21.6 kg. FRR 21:2 MFR 21 Ratio to MFR2.

[0487] FTIR determination of polymer comonomer content (1-hexene)

[0488] The comonomer content was determined based on Fourier transform infrared spectroscopy (FTIR) using a Bruker Tensor 37 spectrometer and OPUS software. Approximately 0.3 g of the sample was compression molded into a circular film with a thickness of 300 μm and a diameter of 28 mm. Silicone paper liners were used on both sides of the film. Do not touch the film with bare hands to avoid contamination. The films were pressed using a Fontijne Pressmodel LabEcon 300. Molding was performed according to the following procedure:

[0489] 4min pre-heating

[0490] 3min 11kN

[0491] 1min 120kN

[0492] Cooling was performed according to the following program with a set point of 15°C:

[0493] 3min 50kN

[0494] The hexene comonomer content is about 1378 cm -1 The absorbance of the reference peak is 2019 cm -1 Use 2cm -1 Resolution from 4000 to 400 cm -1 The analysis was performed over a wavenumber span of 1000 nm and a duration of 16 scans. At least two spectra were obtained from each film.

[0495] Reference peaks are 2100-1980cm -1 , using the integration method G(A) of OPUS software R The baseline of the comonomer area is defined between two points: 1400 cm -1 and 1330cm -1 The baseline is determined using the following method: within the set wave number range, first find the highest peak and then find the minima to the left and right of the highest peak. The baseline connects these minima. Method L of the Opus software is used to calculate the relative to its baseline (A Q The peak intensity of the comonomer (value).

[0496] The hexene content was automatically calculated by OPUS software using the NMR / FTIR calibration curve.The comonomer content in the calibration sample material used to construct the calibration curve was previously determined by NMR spectroscopy.

[0497] The calibration curve is represented by the following equation:

[0498] W NMR =-1.705+46.839·A0

[0499] A0 is the highest peak of the comonomer (relative to the baseline, A Q ) divided by the reference peak area (A R ), provided by OPUS software.

[0500] The comonomer content was determined from the two spectra obtained and is given in % by weight, the value being calculated as the average of these results.

[0501] Bulk density of polymer

[0502] For the example of PE, the bulk density (apparent density) is determined according to ASTM D1895, Method A, using a 100 cm 3 The measuring cup is measured with a measuring device, for PP examples a 20 or 30 cm measuring cup is used according to EN ISO 60. 3 Measured with a measuring cup.

[0503] Determination of polymer melting and crystallization properties by DSC

[0504] The polymer differential scanning calorimetry (DSC) analysis was performed on a TA Instruments Q200 instrument calibrated with indium, zinc and tin with 5 ± 1 mg sample according to ISO 11357 / 1 under nitrogen atmosphere. The polymer powder or MFR-string cut sample was placed in an aluminum pan, weighed to the nearest 0.01 mg, and the pan was sealed with a lid. According to ISO 11357 / 3, the DSC was run between -30°C and 225°C at a scan rate of 10°C / min in a heating / cooling / heating cycle for the first heating, cooling run and second heating. The first melt run was used to remove the thermal history of the sample.

[0505] Crystallization temperature (T c ) is determined by the cooling run, while the main melting temperature (T m ), crystallinity (Cryst.%) and heat of fusion (H m ) is determined by the second heating run.

[0506] Determination of polymer molecular weight and molecular weight distribution by GPC

[0507] The polydispersity index PDI = Mw / Mn (where M n is the number average molecular weight, M w is the weight average molecular weight) describes the average molecular weight (M z 、M w and M n ), molecular weight distribution (MWD) and its breadth are determined by gel permeation chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D6474-12 using the following formula:

[0508]

[0509] For a constant elution volume interval ΔV i , where A i and M i are the chromatographic peak slice area and the molecular weight (MW) of the polyolefin, respectively, and the elution volume V i Correlation, where N equals the number of data points obtained from the chromatogram between the integration limits.

[0510] A high temperature GPC instrument equipped with an infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain)) equipped with 3x Agilent-PLgel Olexis and 1x Agilent-PLgel Olexis guard columns was used. 1,2,4-Trichlorobenzene (TCB) stabilized with 250 mg / L 2,6-di-tert-butyl-4-methylphenol was used as solvent and mobile phase. The chromatographic system was operated at 160°C and a constant flow rate of 1 mL / min. 200 μL of sample solution was injected for each analysis. Data collection was performed using Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

[0511] The column set was calibrated using a universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11500 kg / mol. The PS standards were dissolved at room temperature for several hours. The conversion of polystyrene peak molecular weight to polyolefin molecular weight was done by using the Mark Houwink equation and the following Mark Houwink constants:

[0512] K PS =19x 10 -3 mL / g, α PS =0.655

[0513] K PE =39x 10 -3 mL / g, α PE =0.725

[0514] K PP =19x 10 -3 mL / g, α PP =0.725

[0515] A third-order polynomial fit was used to fit the calibration data.

[0516] All samples were prepared in the concentration range of 0.5-1 mg / mL and dissolved at 160 °C with continuous gentle shaking for 2.5 h for PP or 3 h for PE.

[0517] Polymer xylene soluble matter (gravimetric method)

[0518] The xylene soluble content in polypropylene was determined according to ISO 16152.

[0519] A weighed sample is dissolved in hot xylene under reflux conditions at 135°C. The solution is then cooled under controlled conditions and kept at 25°C for 30 minutes to ensure controlled crystallization of the insoluble component. This insoluble component is then separated by filtration. The xylene is evaporated from the filtrate, leaving the soluble component as a residue. The percentage of this component is determined gravimetrically.

[0520]

[0521] in

[0522] m0 is the mass of the sample tested, in grams

[0523] m1 is the mass of the residue in grams

[0524] v0 is the original volume of the solvent used

[0525] v1 is the volume of the aliquot used for the assay

[0526] Determination of polymer soluble fraction by Crystex

[0527] The crystalline (CF) and soluble fractions (SF) of the polypropylene (PP) compositions as well as the comonomer content and intrinsic viscosity of each fraction were analyzed by CRYSTEX QC Polymer Char (Valencia, Spain).

[0528] A schematic diagram of the CRYSTEX QC instrument is shown in Del Hierro, P.; Ortin, A.; Monrabal, B.; 'Soluble Fraction Analysis in polypropylene, The Column, February 2014. Pages 18-23. The crystalline and amorphous components are separated in a cycle of dissolution at 160°C, crystallization at 40°C and redissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C. Quantification of SF and CF and determination of ethylene content (C2) are achieved by an infrared detector (IR4) and an online double capillary viscometer is used to determine the intrinsic viscosity (IV).

[0529] The IR4 detector is a multi-wavelength detector that detects infrared absorbance in two different bands (CH3 and CH2) and is used to determine the concentration and ethylene content in ethylene-propylene copolymers. A series of known ethylene contents ranging from 2 wt% to 69 wt% (by 13 C-NMR measurement) was performed by calibrating the IR4 detector with EP copolymer.

[0530] The amounts of soluble fraction (SF) and crystalline fraction (CF) were related by performing an XS calibration on the amounts of "xylene cold solubles" (XCS) and xylene cold insolubles (XCI) fractions, respectively, which were determined gravimetrically according to the ISO 16152 standard method. The XS calibration was achieved by testing different EP copolymers with XS contents ranging from 2 to 31 wt%.

[0531] The intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline components were determined using an online 2-capillary viscometer and correlated to the corresponding IV determined according to ISO 1628 in decalin.

[0532] Calibration was achieved using several commercial EP PP copolymers with IV = 2-4 dL / g.

[0533] A sample of the PP composition to be analyzed with a concentration of 10 mg / mL to 20 mg / mL was weighed. After automatically filling the vial with 1,2,4-TCB containing 250 mg / L 2,6-tert-butyl-4-methylphenol (BHT) as an antioxidant, the sample was dissolved by continuous stirring at 160°C at a speed of 800 rpm, usually for 60 minutes until complete dissolution was achieved.

[0534] A defined volume of sample solution is injected into a chromatographic column filled with an inert support, where the sample crystallizes and the soluble components are separated from the crystalline part. This process is repeated twice. During the first injection, the entire sample is measured at high temperature, and the IV [dL / g] and C2 [wt%] of the PP composition are determined. During the second injection, the soluble component (at low temperature) and the crystalline component (at high temperature) (wt% SF, wt% C2, IV) are determined along the crystallization cycle.

[0535] Quantifying microstructure by NMR spectroscopy

[0536] Quantitative nuclear magnetic resonance (NMR) spectroscopy is used to quantify the isotacticity of the polymers.

[0537] Quantitative 13C{1H}NMR spectra were recorded in solution using a Bruker Avance Neo 400MHz NMR spectrometer, operating at 400.15 and 100.63 MHz for 1H and 13C, respectively. All spectra were acquired using 13A C-optimized 10 mm selective excitation probe was recorded at 125 °C, with nitrogen used for all pneumatics. Approximately 200 mg of material was dissolved in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) using approximately 3 mg of 2,6-di-tert-butyl-4-methylphenol (CAS128-37-0) as a stabilizer. Standard 90 degree single pulse excitation was employed using NOE, a two-level WALTZ16 decoupling scheme, a 3 s relaxation delay, and a 10 Hz sample rotation {zhou07, busico07}. A total of 6144 (6k) transients were acquired for each spectrum. This setup was chosen primarily to meet the high resolution required for regularity distribution quantification {busico01, busico97}.

[0538] After processing, integration 13 C{ 1 H} NMR spectra and the relevant quantitative properties were determined from the integration using a proprietary computer program. All chemical shifts were internally referenced to the methyl signal of the isotactic pentad mmmm at 21.85 ppm.

[0539] The stereoregularity distribution was quantified by integrating the methyl region between 23.6 ppm and 19.7 ppm, correcting for any sites not associated with the stereo sequence of interest {busico01,busico97}.

[0540] The pentad tacticity distribution is determined by directly integrating each methyl signal from a given steric pentad individually and then normalizing to the sum of the methyl signals from all steric pentads. The relative content of a particular steric pentad is reported as the mole fraction or percentage of the given steric pentad xxxx relative to all steric pentads:

[0541] [xxxx]=xxxx / (mmmm+mmmr+rmmr+mmrr+xmrx+mrmr+rrrr+mrrr+mrrm)

[0542] where xmrx represents the combined integral of mmrm and rmrr, since the signals from these spatial pentads are usually not resolved. Therefore, the pentad isotacticity is given by:

[0543] [mmmm]=mmmm / (mmmm+mmmr+rmmr+mmrr+xmrx+mrmr+rrrr+mrrr+mrrm)

[0544] The triad tacticity distribution is indirectly determined from the pentad tacticity distribution using the known pentad-triad necessary relationship:

[0545] [mm]=[mmmm]+[mmmr]+[rmmr]

[0546] [mr]=[mmrr]+[xmrx]+[mrmr]

[0547] [rr]=[rrrr]+[mrrr]+[mrrm]

[0548] busico01

[0549] Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443

[0550] busico97

[0551] Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,AL,Macromolecules30(1997)6251

[0552] zhou07

[0553] Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225

[0554] busico07

[0555] Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128

[0556] raw material

[0557] The pretreated silica was a commercial synthetic amorphous silica ES757 obtained from PQ Corp. Pretreatment refers to commercial calcination of silica at 600°C according to conventional PO catalyst technology.

[0558] Methylaluminoxane (30 wt% MAO solution in toluene, Axion CA 1330) was purchased from Lanxess.

[0559] The comparative metallocene complex MC3 is racemic-dimethylsilanediylbis[2-(5-trimethylsilylfuranyl-2-yl)-4,5-dimethylcyclopentadien-1-yl]zirconium dichloride. The complex is prepared in pure stereoisomer form according to the published synthesis procedure (US6326493). Its structure is:

[0560]

[0561] Comparative metallocene complex MC4 is unbridged bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride obtained as a toluene solution from a commercial source.

[0562]

[0563] The following metallocene was prepared:

[0564] The metallocene complex MC1 of the present invention (racemic or trans) and the comparative metallocene MC5 (meso or cis)

[0565]

[0566] Multi-step preparation:

[0567] trans- and cis-methyl(pent-4-en-1-yl)silanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

[0568] Bis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopenta-2,4-dien-1-yl](methyl)penta- 4-Ethyl-1-silane

[0569]

[0570] To a solution of 19.6 g (84.3 mmol) of 1-(2-(5-trimethylsilyl)furyl)-3,4-dimethylcyclopentadiene dissolved in 200 ml of THF cooled to -78°C was added 34.7 ml (84.3 mmol) of 2.43 M nBuLi hexane solution. The resulting red solution was stirred at room temperature for 4 hours, then cooled to -50°C and 300 mg of CuCN was added. The resulting mixture was stirred at -25°C for 15 minutes, and then 7.72 g (42.2 mmol) of dichloro(methyl)pent-4-en-1-ylsilane was added in one portion. The mixture was stirred at room temperature overnight. The solvent was removed on a rotary evaporator; 600 ml of dichloromethane was added to the dark red residue, and the resulting mixture was washed with 600 ml of water. The organic layer was separated, dried over Na2SO4, filtered through a silica gel pad 60 (40-63 um), and washed with 2×50 ml of dichloromethane. The combined filtrate was distilled under reduced pressure and dried in vacuo to obtain 21.9 g (90%, purity about 75%) of the target product as a dark red oil (containing a mixture of two stereoisomers in about 60:40).

[0571] trans- and cis-methyl(pent-4-en-1-yl)silanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furan [(4,5-dimethylcyclopentadienyl)zirconium dichloride]

[0572]

[0573] 31.3 ml (76.1 mmol) of 2.43 M bis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopenta-2,4-dien-1-yl](methyl)pent-4-en-1-ylsilane was added to a solution of 21.85 g (about 28.5 mmol) of bis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopenta-2,4-dien-1-yl](methyl)penta-4-en-1-ylsilane dissolved in 250 ml of diethyl ether and cooled to -78°C. nBuLi hexane solution. The mixture was stirred at room temperature for 4 hours, then the resulting red solution was cooled to -78°C and 8.86 g (38.02 mmol) of ZrCl4 was added. The mixture was stirred at room temperature for 20 hours (obtaining a dark red solution with a yellow precipitate) and then evaporated to dryness. The residue was stirred with 100 ml of hot toluene and the resulting suspension was filtered through a glass frit (G4). According to the evidence of NMR spectra, the filtrate contained a mixture of isomeric complexes, i.e., a trans-complex and two isomeric cis-zirconocenes in a ratio of 2:1:1. The filtrate was evaporated to dryness and the residue was dissolved in a mixture of 25 ml of n-hexane and 100 ml of n-pentane. The yellow solid precipitated from the solution overnight at -30°C was filtered out (G4) and dried in vacuo. This step yielded 3.90 g of a trans-complex contaminated with a cis-complex. The sample was recrystallized in a mixture of 10 ml toluene and 30 ml n-hexane to obtain 3.00 g of pure trans-dichlorodizirconocene. The mother liquor (obtained after separating 3.90 g of sample) was evaporated to dryness and the residue was dissolved in 100 ml n-pentane. The yellow solid precipitated from the resulting solution overnight at -30°C was filtered out (G4) and dried in vacuo to obtain 1.85 g of the trans-isomer containing traces of one of the two cis complexes. Finally, the mother liquor was evaporated to a black foam state, which was then dissolved in 150 ml n-pentane. The yellow precipitate precipitated from the solution at -30°C for 2 days was filtered out (G4), washed with 5 ml of toluene and dried in vacuo to obtain 2.10 g of a 45:55 mixture of trans- and cis-complexes. Recrystallization of the mixture from a mixture of n-hexane and n-pentane gave 0.23 g of one of the two cis complexes contaminated with about 6% of the trans-isomer. Thus, the total yield of the trans and cis complexes was 7.85 g (37.5%). It should be noted that only one of the two cis-isomers was isolated in this reaction. trans-methyl(pent-4-en-1-yl)silanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

[0574] C 34 H 48 Theoretical calculation of Cl2O2Si3Zr: C, 55.55; H, 6.58. Experimental value: C, 55.81; H, 6.70.

[0575] 1H NMR (CDCl3): δ6.71 (2s, 2H), 6.61 (d, J = 3.2Hz, 2H), 6.56 (d, J = 3.2Hz, 1H), 6. 52(d,J=3.2Hz,1H),5.90-5.77(m,1H),5.04(dm,J=17.1Hz,1H),4.98(dm,J= 10.2Hz,1H),2.28-2.10(m,2H),2.19(s,6H),1.85-1.59(m,2H),1.48(s,3H) ,1.46(s,3H),1.21(t,J=8.4Hz,2H),0.73(s,3H),0.29(s,9H),0.28(s,9H). 13 C{ 1 H}NMR(CDCl3): δ159.81,159.56,153.28,153.20,138.54,138.31,138.02,129.57,129.13,128.51,127.78,123.06,122.11, 121.82,121.74,114.96,110.30,110.17,99.93,99.75,37.22,22.79,16.84,14.47,14.31,14.25,14.00,0.42,-1.24,-1.39.

[0576] cis-methyl(pent-4-en-1-yl)silanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

[0577] C 34 H 48 Theoretical calculation of Cl2O2Si3Zr: C, 55.55; H, 6.58. Experimental value: C, 55.69; H, 6.76.

[0578] 1 H NMR (CDCl3): δ6.63 (s, 2H), 6.31 (d, J = 3.2Hz, 2H), 6.11 (d, J = 3.2Hz, 2H), 5.93-5.80 (m, 1H), 5.09 (dm, J = 17.1Hz, 1H), 5.04 (dm, J=10.2Hz,1H),2.31-2.23(m,2H),2.28(s,6H),2.00(s,6H),1.85-1.73(m,2H),1.53-1.45(m,2H),0.40(s,3H),0.22(s,18H). 13 C{ 1H}NMR(CDCl3): δ158.57,152.38,138.09,138.06,131.29,129.02,122.74,12 1.42,115.44,110.23,99.49,37.28,22.76,16.54,15.17,14.32,0.34,-1.40.

[0579] The metallocene complex MC2 of the present invention

[0580]

[0581] Multi-step preparation:

[0582] Racemic-dimethylsilanediyl-bis[η 5 -2-(2-(5-dimethylphenylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

[0583] 2-Furyl(dimethyl)phenylsilane

[0584]

[0585] To a solution of 25.0 g (367 mmol) of furan dissolved in 165 ml of ether cooled in an ice bath was added dropwise 123.5 ml (300 mmol) of 2.43 M n BuLi in hexane. The resulting mixture was stirred at room temperature for 3.5 hours, then the resulting suspension was cooled to -78°C, and 50.0 ml (51.6 g, 302 mmol) of dimethylphenylsilyl chloride was added at once. The resulting mixture was stirred at room temperature for 40 hours. The resulting suspension was filtered through a silica gel pad 60 (40-63 um) and washed with 3×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the residue was vacuum distilled (boiling point 79°C / 3-4 mm Hg) to obtain 56.6 g (93%) of 2-furyl (dimethyl) phenylsilane as a colorless liquid.

[0586] 1 H NMR (CDCl3): δ7.67 (d, J = 1.6 Hz, 1H), 7.58-7.53 (m, 2H), 7.38-7.33 (m, 3H), 6.67 (d, J = 3.2 Hz, 1H), 6.38 (dd, J = 3.2 Hz, J = 1.6 Hz, 1H), 0.54 (s, 6H). 13 C{ 1 H}NMR(CDCl3): δ158.14,147.11,136.95,133.91,129.37,127.85,121.02,109.41,-2.91.

[0587] 1-[2-(5-Dimethylphenylsilyl)furyl]-3,4-dimethylcyclopenta-1,3-diene

[0588]

[0589] To a solution of 20.2 g (100 mmol) of 2-furyl(dimethyl)phenylsilane dissolved in 150 ml of THF cooled to -78°C was added dropwise 41.2 ml (100.1 mmol) of 2.43 M n BuLi hexane solution. The resulting mixture was stirred at room temperature for 20 hours, then cooled to -30°C, and a solution of 11.0 g (100 mmol) of 3,4-dimethylcyclopent-2-en-1-one dissolved in 60 ml of THF was added dropwise under vigorous stirring. The resulting solution was stirred at room temperature overnight, then cooled in an ice bath, and 200 ml of 5N HCl was added. The mixture was transferred to a separatory funnel, 600 ml of ether was added, and the resulting mixture was shaken for 1 minute. The organic layer was separated, washed with 3×150 ml of water, dried over Na2SO4, and then evaporated to dryness (plus concentration). The residue was adsorbed on silica gel 60 (40-63 um; eluent: hexane) and purified by flash column chromatography to obtain 25.9 g (88%, purity about 90%) of the target product as a slightly reddish oily liquid.

[0590] 1 H NMR(CDCl3): δ7.59-7.56(m,2H),7.38-7.33(m,3H),6.62(d,J=3.2Hz,1H),6.57(br .s,1H),6.21(d,J=3.2Hz,1H),3.21(s,2H),1.94(s,3H),1.87(s,3H),0.54(s,6H). 13 C{ 1 H}NMR(CDCl3): δ157.01,156.14,137.36,135.34,135.14,133.97,132.8 9,131.37,129.24,127.80,122.95,104.15,44.75,13.35,12.54,-2.75.

[0591] Bis[2-(2-(5-dimethylphenylsilyl)furyl)-4,5-dimethylcyclopenta-2,4-dien-1-yl]dimethyl Silane

[0592]

[0593] To a solution of 25.9 g (87.9 mmol) of 1-[2-(5-dimethylphenylsilyl)furyl]-3,4-dimethylcyclopenta-1,3-diene dissolved in 200 ml of THF cooled to -78°C was added 36.2 ml (88.0 mmol) of 2.43 M n BuLi in hexane.

[0594] The resulting dark red solution was stirred at room temperature for 3 hours, then cooled to -50°C and 300 mg of CuCN was added. The resulting mixture was stirred at -25°C for 15 minutes, then 5.67 g (55.56 mmol) of dichlorodimethylsilane was added in one portion. The mixture was stirred at room temperature overnight. The solvent was removed on a rotary evaporator; 700 ml of dichloromethane was added to the dark red residue, and the resulting mixture was washed with 800 ml of water. The organic layer was separated, dried over Na2SO4, and filtered through a silica gel pad 60 (40-63 um), which was washed with 2×50 ml of dichloromethane. The combined filtrates were evaporated under reduced pressure and the residue was dried in vacuo to obtain 25.6 g (90%, purity about 80%) of the target proligand (containing a mixture of two stereoisomers about 1:1) as a dark red oil.

[0595] 1 H NMR (CDCl3): δ7.57-7.46(m,4H),7.39-7.26(m,6H),6.59(d,J=3.2Hz),6.57(br.s)and 6.57(d,J=3.2Hz){sum 4H},6.24(d,J=3.2Hz)and 6.07(d,J=3.2Hz){sum2H},4.07(s)and 3.70(s){sum 2H},2.13(s),1.98(s),1.88(s)and 1.87(s){sum 12H},0.51(s),0.50(s),0.48(s)and 0.46(s){sum 12H},-0.45(s),-0.72(s)and-0.78(s){sum6H}.

[0596] Racemic-dimethylsilanediyl-bis[η 5 -2-(2-(5-dimethylphenylsilyl)furanyl)-4,5-dimethyl Cyclopentadienyl]zirconium dichloride

[0597]

[0598] To a solution of 25.6 g (about 39.7 mmol) of bis[2-(2-(5-dimethylphenylsilyl)furyl)-4,5-dimethylcyclopenta-2,4-dien-1-yl]dimethylsilane in 300 ml of diethyl ether cooled to -78°C was added 32.6 ml (79.2 mmol) of 2.43 M nA solution of BuLi in hexane. The mixture was stirred at room temperature overnight, and then the obtained brown suspension with a large amount of white precipitate was cooled to -78°C, and 9.25g (39.7mmol) ZrCl4 was added. The reaction mixture was stirred at room temperature for 24 hours to obtain a dark red solution containing a yellow precipitate. The precipitate was filtered out. The filtrate was evaporated to about 30 ml, and then 30 ml of n-hexane was added. The yellow powder precipitated from the mixture (a mixture of the target complex and LiCl) was filtered out, washed with n-hexane, and then added to the above-mentioned separated precipitate. The residue was stirred with 50ml of hot toluene (almost under reflux), and the suspension formed was filtered through a glass frit (G4). The filtrate was evaporated to about 25ml, heated to about 60°C, and then 30ml of n-hexane was added. The yellow powder precipitated from the solution overnight at room temperature (G4) was filtered out and vacuum dried to obtain 4.82g of the target complex. The mother liquor was evaporated to about 5ml and 25ml of hexane was added. The yellow solid (G4) which precipitated overnight at room temperature from the mixture thus obtained and was not filtered off was collected and then dried in vacuo. This step yielded an additional 0.7 g of the title zirconocene. The total yield of the target racemic complex was thus 5.52 g (17%).

[0599] C 40 H 46 Theoretical calculation of Cl2O2Si3Zr: C, 59.67; H, 5.76. Experimental value: C, 59.95; H, 5.81.

[0600] 1 H NMR(CDCl3): δ7.58-7.52(m,2H),7.41-7.31(m,3H),6.69(s,1H),6.65(d,J=3.3Hz,1H), 6.55(d,J=3.3Hz,1H),2.16(s,3H),1.35(s,3H),0.56(s,3H),0.55(s,3H),0.54(s,3H). 13 C{ 1 H}NMR(CDCl3): δ157.60,154.01,138.23,136.56,134.06,129.42,128.77,128. 18,127.80,123.41,122.01,110.19,100.06,14.22,14.18,3.34,-2.65,-3.05.

[0601] Comparative Examples Metallocene Complex MC6 and Metallocene MC7

[0602]

[0603]

[0604] Multi-step preparation:

[0605] Racemic-dimethylsilanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4-tert-butylcyclopentadienyl]zirconium dichloride

[0606] 2-Acetyl-5,5-dimethyl-4-oxohexanoic acid ethyl ester

[0607]

[0608] 12.5 g (544 mmol, 1.66 chemical equivalents) of sodium were added to 360 ml of toluene, followed by 132 ml (1.04 mol, 3.16 chemical equivalents) of ethyl acetoacetate. A violent exothermic reaction occurred after one minute with the release of hydrogen, which subsided after about 10 minutes. The reaction mixture was then stirred at room temperature for 2 hours. 58.8 g (329 mmol) of 1-bromo-3,3-dimethylbutan-2-one was added dropwise to the resulting heterogeneous mixture, and the reaction mixture was stirred at room temperature overnight. The resulting mixture was cooled in an ice bath and then treated with 400 ml of water. Another 400 ml of water was added, the organic layer was separated, and the aqueous layer was extracted with 400 ml of ether. The combined organic extracts were dried over Na2SO4, evaporated, and the excess ethyl acetoacetate was removed by vacuum distillation (bp≤65°C / 6 mm Hg) to obtain 79.3 g (about 100%) of the target product, which was used further without additional purification.

[0609] 1 H NMR (CDCl3): δ4.19 (q, J=7.2Hz, 2H), 4.01 (dd, J=8.3Hz, J=5.6Hz, 1H), 3.23 (dd, J=18.5Hz, J=8 .3Hz,1H),3.02(dd,J=18.5Hz,J=5.6Hz,1H),2.37(s,3H),1.28(t,J=7.2Hz,3H),1.17(s,9H). 13 C{ 1 H}NMR(CDCl3): δ213.36,202.49,168.92,61.57,53.67,43.77,35.70,30.18,26.39,13.95.

[0610] 3-tert-Butylcyclopent-2-en-1-one

[0611]

[0612] 1L of hot water was added to 37.5g (164.3mmol) of 2-acetyl-5,5-dimethyl-4-oxohexanoate (prepared as above). A solution of 110g (1.96mol) of KOH in 500ml of water was added dropwise to the mixture under reflux for more than 1 hour. The reaction mixture was refluxed for 8 hours, cooled to room temperature, and then extracted with 3×400ml of ether. The combined extracts were dried over Na2SO4, filtered through a silica gel pad 60 (40-63um), and then evaporated to dryness to obtain 18.0g of 6,6-dimethylheptane-2,5-dione with about 15% 1 The crude products obtained from four similar syntheses were combined and vacuum distilled to obtain 3-tert-butylcyclopentane-2-ene-1-one fractions of different purities, including a 3-tert-butylcyclopentane-2-ene-1-one fraction with a purity of about 95%, which has a higher boiling point than 6,6-dimethylheptane-2,5-dione. Therefore, the calculated yield of the target product (based on 1 H NMR data confirmed the purity of 3-tert-butylcyclopentane-2-en-1-one) to be 52.0 g (57%), while 6,6-dimethylheptane-2,5-dione-8.77 g (8.5%). The results showed that the mixture of 3-tert-butylcyclopent-2-en-1-one and dione could be used for the subsequent synthesis of substituted cyclopentadiene.

[0613] 1 H NMR (CDCl3): δ5.95 (t, J=1.7Hz, 1H), 2.67-2.63 (m, 2H), 2.44-2.40 (m, 2H), 1.2 (s, 9H). 13 C{ 1 H}NMR(CDCl3): δ210.54,191.11,127.21,35.41,35.11,28.68,27.58.

[0614] 1-tert-Butyl-3-[2-(5-trimethylsilyl)furyl]cyclopenta-1,3-diene

[0615]

[0616] To a solution of 22.2 g (158 mmol) of 2-trimethylsilylfuran dissolved in 230 ml of THF cooled to -78°C was added dropwise 65.2 ml (158 mmol) of 2.43 M nBuLi in hexane. The resulting mixture was stirred at room temperature for 7.5 hours, then cooled to -35°C, and 20.0 g of 89% pure 3-tert-butylcyclopent-2-en-1-one [containing about 11% of 6,6-dimethylheptane-2,5-dione, so the added mixture contained 17.55 g (127 mmol) of 3-tert-butylcyclopent-2-en-1-one and 2.45 g (15.68 mmol) of 6,6-dimethylheptane-2,5-dione] was added in one portion. The resulting solution was stirred at room temperature overnight, then cooled in an ice bath, and 200 ml of 4N HCl was added. The mixture was transferred to a separatory funnel, 500 ml of ether was added, and the resulting mixture was shaken for 1 minute. The organic layer was separated, washed with 3×200 ml of water, dried over Na2SO4, and then evaporated to dryness. The residue was purified by flash column chromatography using silica gel 60 (40-63 um; eluent: hexane) to give 27.5 g (83%, based on 3-tert-butylcyclopent-2-en-1-one in the mixture) of the target product (a mixture of two double bond regioisomers in a ratio of approximately 88:12) as an orange oily liquid that spontaneously solidified at room temperature.

[0617] 1 H NMR (CDCl3): δ6.83(m,1H),6.59(d,J=3.2Hz,1H),6.27(d,J=3.2Hz,1H),5.89(“q”,J=1.7Hz,1H),3.27(“t”,J=1.4Hz,2H),1.2(s,9H),0.28(s,9H). 13 C{ 1 H}NMR(CDCl3): δ158.86,157.62,156.36,137.02,127.12,121.29,121.01,104.93,40.01,32.20,29.70,-1.48.

[0618] Bis[2-(2-(5-trimethylsilyl)furyl)-4-tert-butylcyclopenta-2,4-dien-1-yl]dimethylsilane

[0619]

[0620] To a solution of 25.5 g (97.9 mmol) of 1-tert-butyl-3-[2-(5-trimethylsilyl)furyl]cyclopentadiene-1,3-diene dissolved in 200 ml of THF cooled to -50°C was added 40.3 ml (97.9 mmol) of 2.43 M nBuLi in hexane. The dark red solution was stirred at room temperature for 3.5 hours, then cooled to -50°C and 300 mg of CuCN was added. The mixture was stirred at -25°C for 15 minutes, then 6.32 g (49.0 mmol) of dichlorodimethylsilane was added at once. The mixture was stirred at room temperature overnight. The solvent was removed on a rotary evaporator; 600 ml of dichloromethane was added to the dark red residue, and the mixture was washed with 800 ml of water. The organic layer was separated, dried over Na2SO4, filtered through a silica gel pad 60 (40-63 um), and washed with 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure. The dark red oil was dissolved in 500 ml of n-hexane, and the suspension was filtered through a silica gel pad 60 (40-63 um), and washed with 3×50 ml of n-hexane. The filtrate was evaporated and dried in vacuo to give 25.4 g (90%, purity about 90%) of bis[2-(2-(5-trimethylsilyl)furanyl)-4-tert-butylcyclopenta-2,4-dien-1-yl]dimethylsilane (a mixture of two stereoisomers in a ratio of about 1:1) as a light red oil.

[0621] 1 H NMR (CDCl3): δ6.85-6.82(m,2H),6.58(d,J=3.2Hz)and 6.57(d,J=3.2Hz){sum 2H},6.29(d,J=3.2Hz)and 6.27(d,J=3.2Hz){sum 2H},6.17(m)and 6.11(m){sum2H},3.87(d,J=1.2Hz)and 3.66(d,J=1.2Hz){sum2H},1.24(s)and 1.19(s){sum 18H},0.23(s)and 0.22(s){sum 18H},-0.36(s),-0.44(s)and-0.50(s){sum 6H}. 13 C{ 1 H}NMR(CDCl3): δ158.41,158.40,156.50,156.43,156.09,155.78,138.14,138.03,126.69,126.59,124.53,123.75,121.37(two resonances),104.90,104.82,48.75,47.78,32.30,32.24,30.41,30.38,-1.43,-1.46,-4.29,-6.52,-6.76.

[0622] Racemic- and meso-dimethylsilanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furanyl)-4-tert- [butylcyclopentadienyl]zirconium dichloride

[0623]

[0624] To a solution of 25.4 g (about 44.0 mmol) of bis[2-(2-(5-trimethylsilyl)furyl)-4-tert-butylcyclopenta-2,4-dien-1-yl]dimethylsilane dissolved in 350 ml of diethyl ether cooled to -78°C was added 36.2 ml (88.0 mmol) of 2.43 M n Hexane solution of BuLi. The mixture is stirred at room temperature overnight, then the resulting red solution is cooled to -78°C and 10.3 g (44.2 mmol) of ZrCl4 is added. The reaction mixture is stirred at room temperature for 24 hours to obtain a dark red solution and a yellow precipitate. The mixture is evaporated to dryness. The residue is stirred with 200 ml of hot toluene and the resulting suspension is filtered through a glass frit (G4). The filtrate is evaporated to about 100 ml. The light orange precipitate precipitated from the solution at room temperature for 3 hours is washed with 10 ml of toluene and then dried in vacuo. This step yields 9.70 g (30%) of pure racemic complex. The mother liquor is evaporated to about 10 ml, the resulting solution is heated to about 60°C, and then 30 ml of n-hexane is added. The yellow powder (meso complex contaminated with 5% racemic isomer) and red crystals (mixture of racemic and meso compounds in a ratio of about 4:1) precipitated from the solution at room temperature overnight were filtered (G4) to obtain 9.30 g of meso zirconocene contaminated with about 15% racemic complex. The mother liquor was evaporated to dryness and the residue was dissolved in 40 ml of n-hexane. The yellow solid precipitated from the resulting mixture overnight at room temperature was filtered out (G4) and dried in vacuo. This step obtained 3.50 g of a mixture of meso / racemic complexes in a ratio of 67:43. Therefore, the total yield of racemic and meso dichlorozirconocene was 22.5 g (69%). 120 ml of n-hexane was added to the yellow powder from the second component (9.30 g, yellow powder with red crystals), the yellow powder dissolved quickly, and the red crystals were immediately filtered out (G3). The filtrate was evaporated to dryness and the residue was recrystallized from a mixture of 7 ml toluene and 15 ml n-hexane to give 4.50 g (14%) of pure meso-dimethylsilanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4-tert-butylcyclopentadienyl]zirconium dichloride.

[0625] Racemic-dimethylsilanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4-tert-butylcyclopentadienyl]zirconium dichloride.

[0626] C 34 H 50Theoretical calculation of Cl2O2Si3Zr: C, 55.40; H, 6.84. Experimental value: C, 55.64; H, 7.02.

[0627] 1 H NMR (CDCl3): δ6.75(d,J=2.5Hz,2H),6.67(d,J=3.3Hz,2H),6.54(d,J=3.3Hz,2H),5.54(d,J=2.5Hz,2H),1.26(s,18H),0.84(s,6H),0.33(s,18H). 13 C{ 1 H}NMR(CDCl3): δ159.89,153.94,153.36,124.98,123.70,122.07,111.58,109.47,103.22,33.89,30.16,-0.09,-1.31.

[0628] Meso-dimethylsilanediyl-bis[η 5 -2-(2-(5-trimethylsilyl)furyl)-4-tert-butylcyclopentadienyl]-zirconium dichloride (this stereoisomer was not used in the catalyst preparation and polymerization examples).

[0629] C 34 H 50 Theoretical calculation of Cl2O2Si3Zr: C, 55.40; H, 6.84. Experimental value: C, 55.77; H, 7.09.

[0630] 1 H NMR(CDCl3): δ6.82(d,J=2.5Hz,2H), 6.25(d,J=3.3Hz,2H), 6.07(d,J=3.3Hz,2H ),5.69(d,J=2.5Hz,2H),1.35(s,18H),1.04(s,3H),0.74(s,3H),0.28(s,18H). 13 C{ 1 H}NMR(CDCl3): δ158.44,152.94,152.89,127.08,124.46,122.28,111.97,108.47,101.59,34.10,30.35,1.77,-1.36,-2.89.

[0631] The complexes MC1 to MC2 of the present invention are:

[0632] Trans-form The metallocene of the comparative example in racemic-form is:

[0633] Racemic-form

[0634] Meso-form

[0635] Racemic-form

[0636] Catalyst preparation

[0637] All catalyst examples were prepared using the following “General One-Step Catalyst Preparation Method” and are summarized in Table 1.

[0638] Table 1: Catalyst Examples and Comparative Examples of the Present Invention

[0639]

[0640] Universal one-step catalyst preparation method

[0641] The pre-contacted mixture obtained by dissolving 140 μmol of metallocene in methylaluminoxane solution (30 wt% MAO in toluene containing 14 mmol Al) and 1.6 mL of additional toluene was stirred in a glass vial at room temperature under nitrogen atmosphere for 2 hours. The obtained solution was then added dropwise to 2 g of pretreated silica support in a glass reactor over 5 minutes under gentle mechanical stirring at 10-30° C. The crude catalyst was then gently mixed for another hour and allowed to stand for another 17 hours. The catalyst was then dried under vacuum at 60° C. for 60 minutes.

[0642] Polymerization experiment 1: Unimodal ethylene / 1-hexene copolymerization

[0643] All catalyst examples were tested in slurry phase ethylene copolymerization using the following “Conventional Laboratory Scale Ethylene Slurry Phase Copolymerization Procedure” and the corresponding examples are summarized in Table 2.

[0644] General laboratory scale ethylene slurry phase copolymerization process

[0645] The scavenger feed vessel was filled with 1.5 mL triisobutylaluminum (TiBA; 10% in heptane) and connected to the polymerization reactor. The TiBA solution was added to the empty reactor using N2 pressure (5.0 bar). After the TiBA feed, the reactor pressure was reduced to 0.2 bar of N2.

[0646] The reactor was filled with 1250 mL of liquid propane at 20°C and the reactor pressure was 8.92 bar.

[0647] At a stirring rate of 350 rpm, the reactor was heated to the desired prepolymerization temperature of 60° C. The pressure in the reactor was 21.95 bar.

[0648] 0.2 bar H2 from a 500 mL container was filled into the line. Ethylene (32.6 g) and 1-hexene (5.0 mL / 3.4 g) corresponding to a pressure difference of 3.70 bar were added to the reactor through the line containing H2. The pressure in the reactor was increased to 25.65 bar.

[0649] The required amount of catalyst (usually 25-35 mg) was weighed into the catalyst feeder in the glove box. The catalyst feeder was connected to the polymerization reactor and the air in the pipeline was removed by 3 repeated cycles of vacuum and N2 filling. After the pipeline was inerted, the catalyst was flushed into the reactor with 100 mL of propane and the stirring speed was increased to 550 rpm. The pressure in the reactor was about 25.61 bar.

[0650] The prepolymerization step was continued, keeping the pressure constant by feeding ethylene using a flow meter, until 2-5% of prepolymerized material was formed at 60° C. (roughly corresponding to 2-5 g of C2 consumption). Typically, about 40 minutes were required to achieve the desired degree of prepolymerization.

[0651] The temperature of the polymerization reactor was increased to 85°C resulting in a reactor pressure of 40.4 bar.

[0652] 0.2 bar H2 from a 500 mL vessel was filled into the line. Ethylene (62.5 g) and 1-hexene (10.0 mL / 6.7 g) corresponding to a pressure difference of 6.70 bar were added to the reactor through the line containing H2.

[0653] For the slurry polymerization step, the reactor was stirred at 85°C for 60 minutes. The pressure was kept constant by feeding ethylene through a flow meter. After 60 minutes of polymerization, the reaction was stopped by reducing the stirring speed to 150 rpm, venting the reactor and reducing the temperature to 60°C. To remove hydrocarbon residues (before opening) - the reactor was flushed 10 times by pressurizing / releasing 1 bar of nitrogen pressure. The reactor was cooled to 20°C before opening.

[0654] Table 2: Ethylene / 1-hexene copolymerization of the examples of the present invention and comparative examples.

[0655] Aggregate Instance IE1-1 IE2-1 CE1-1 CE2-1 CE3-1 CE4-1 Catalyst used IC1 IC2 CC1 CC2 CC3 CC4 Metallocene in Catalyst MC1 MC2 MC3 MC4 MC5 MC6 <![CDATA[Activity, kg PE / (g cat *h)]]> 6.3 3.8 2.8 1.6 2.7 0.5 1-Hexene incorporation, wt% 4.2 4.2 3.9 1.0 2.0 1.3 <![CDATA[MFR 21 ,g / 10min]]> 59.7 41.8 59.2 113.5 85 - <![CDATA[MFR2,g / 10min]]> 2.2 1.8 2.7 5.5 1.6 47 <![CDATA[FRR 21:2 ]]> 27.1 23.2 21.9 20.6 53.1 - <![CDATA[Bulk density, g / cm 3 > 0.36 0.38 0.37 0.38 0.37 0.38

[0656] The inventors surprisingly found that when the metallocene complexes of the present invention were heterogeneously phased in the manner described to provide IC1 and IC2 of the present invention, superior catalyst activity was observed compared to CC1-CC4 ( Figure 1), comonomer sensitivity ( Figure 2 ), M w ability( Figure 3 ) and dynamics ( Figure 6 ).

[0657] Crucially, IC1 and IC2 combine to form a w ability, high comonomer sensitivity, high activity ( Figure 4 and Figure 5 ) and stable dynamics ( Figure 6 ).

[0658] from Figure 1 It can be seen that the catalytic activities of IC1 and IC2 in polymerization examples IE1-1 and IE2-1 are increased by 126% and 35% compared to CC1 (Example CE1-1). The increase in activity of IC1 is particularly prominent under beating conditions (IE1-1). This increase in activity is attributed to the presence of long alkenyl chains in the metallocene structure (compare MC1 and MC3 from CC1). The use of alkenyl chains has never been used before in furanyl substituted bridged bis-CPs.

[0659] The inventors also found that this effect becomes insignificant for the more open meso form, as demonstrated by the differently (poorly) performing CC3 (complex MC5, which otherwise has the same structure as MC1 from IC1). Similar performance-reducing effects for the meso form are not universal, but have been experienced at least for the meso isomers of MC3 and MC6. Comparison of examples IE1-1 with CE3-1 demonstrates the importance of selectively utilizing pure stereoisomeric forms to obtain optimal performance. The halving of the comonomer sensitivity of CC3 compared to IC1 suggests that more sterically shielded structures are superior to the more open meso form.

[0660] Comparison of IE1-1 and IE2-1 with CE4-1 demonstrates the importance of careful selection of metallocene architecture, such as substituent patterns within the same metallocene type, when focusing on high performance. Even though the furanyl moiety of the metallocene is exactly the same as IC1, the performance of CC4 is very low. It reveals that the introduction of a large substituent at position 4 of the Cp ring, rather than two small substituents at positions 4 and 5, sterically hinders the access of the metal center, rendering this complex ineffective in ethylene polymerization.

[0661] The inferior performance of CC2 (unbridged bis-Cp complex MC4) shows that the furanyl-substituted bridged bis-Cp complexes themselves have an overall strong advantage over unbridged bis-Cp complexes when heterogenized and activated in the same manner. In this regard, especially in terms of copolymer molecular weight and comonomer incorporation, the potential of bridged furanyl-based bis-Cp examples is enormous compared to common commercial bis-Cp examples.

[0662] Figure 2 It is shown that the comonomer sensitivity of IC1 and IC2 is increased by 7% compared to CC1. Such an increase is usually closely related to the metallocene structure. Therefore, a 7% increase is a satisfactory achievement that can benefit the economics of the polymerization process.

[0663] Figure 3 The M values ​​of MC1 and MC2 (catalyst examples IC1 and IC2) under the copolymerization conditions used are shown. w Capability compared to MC3 (CC1) M w The capacity is increased, and the MFR2 value is reduced by 68% compared to MC4 (catalyst CC2). This provides the potential use of the new catalyst for the production of certain copolymer grades that are not available with ordinary unbridged Zr-based bis-CPs.

[0664] It is the above effects and improved performance ( Figure 4 and Figure 5 The combination of higher activity and improved comonomer sensitivity with higher M w This combination of capabilities is critical to the economic viability of a catalyst.

[0665] Figure 6 Not only the superior catalyst performance in IE1-1 and IE2-1 was demonstrated, but also the desired stable polymerization kinetics profiles were shown. The higher performance of IE1-1 within the first 40 min of the experiment reflects the higher activity of IC1 in the prepolymerization step.

[0666] Polymerization experiment 2: Unimodal propylene homopolymerization

[0667] All catalyst examples (excluding CC2) were tested for propylene homopolymerization in propylene bulk using the following “General Propylene Bulk Phase Homopolymerization Method” and the corresponding examples are summarized in Table 3.

[0668] General propylene bulk phase homopolymerization process

[0669] Propylene homopolymerization was carried out in a 0.48 L autoclave in bulk phase. Before the experiment started, the reactor was inerted and purged with propylene. 25 mL (1.1 mmol) of hydrogen was added in batches to the empty reactor. 280 mL of liquid propylene was charged into the reactor at 20 ° C and 10.5 bar pressure. 100 μL of triethylaluminum (TEA; 0.25 mol / L heptane solution) was added as a scavenger using nitrogen (0.7 bar). The contact time between propylene and TEA was 20 minutes. The stirring speed was 350 rpm and kept constant throughout the experiment.

[0670] The dry catalyst (40-50 mg) was weighed into a catalyst vial and suspended in heptane (solid content = 6.7-8.3 mg / mL). Using nitrogen (0.7 bar), an aliquot of the catalyst / heptane slurry was injected into the prepared reactor, so that there was a total amount of 16-20 mg of catalyst in the reactor. The prepolymerization step was carried out at 20° C. and a total pressure of 11.6 bar for 20 minutes. The reactor was then heated to the main bulk polymerization temperature of 80° C. within 7-10 minutes. The bulk polymerization was carried out at 80° C. and a total pressure of 36.5 bar for 60 minutes. In the case of low catalyst activity, the polymerization time was extended to 120 minutes.

[0671] The polymerization was stopped by cooling the reactor to ambient temperature, reducing the stirrer speed to 20 ppm, flushing the reactor and adding an O2 / N2 (1% O2) gas mixture up to 76 bar. The reactor was evacuated and a flushing procedure (vacuum, N2>7 bar-vacuum, repeated several times) was applied to remove the remaining propylene. The polymer powder was stably removed using 2500 ppm of Irganox B225 (dissolved in acetone) and dried naturally in a fume hood.

[0672] The polymerization experiments for each catalyst were repeated twice. Table 3 summarizes the average polymerization results and polymer characterization data (including MFR, GPC, DSC, solution NMR, XCS and Crystex).

[0673] Table 3: Propylene homopolymerization results

[0674]

[0675]

[0676] Surprisingly, it was found that MC1 and MC2 can also be polymerized under propylene polymerization conditions (Examples of the present invention). The inventors surprisingly found that when the metallocene complexes of the present invention are heterogeneously phased to obtain IC1 and IC2 of the present invention in the manner described, such as Figure 7 As shown in Figure 2, the catalyst activities of IE1-2 and IE2-2 were increased by 45% and 36% respectively compared with CE1-2. A good powder morphology with mostly spherical polypropylene particles and a particle size greater than 0.4 g / cm 3 Examples CE3-2 and CE4-2 show significantly lower activity and poorer morphology than CE1-2. The result of CE3-2 (produced by comparative catalyst CC3 based on meso complex MC5) is a completely amorphous oily polymer material, while CE4-2 represents irregular polymer flakes with partially molten agglomerates.

[0677] according to Figure 8IE2-2 showed higher activity and higher weight average molecular weight (M) than CE1-2. w ), while IE1-2 showed higher activity but lower M than CE1-2. w Compared with IC1, IC2 and CC1, the catalysts of CC3 and CC4 have the lowest M w ability.

[0678] according to Fig. 9 and Fig.10 , IE1-2 and IE2-2 experiments produced comparable PP isotacticity and soluble fractions. CE3-2 provided very low isotacticity and very high soluble fractions, which are reflected in the highly amorphous, oily nature of the above polymers. CE4-2 also showed lower isotacticity and significantly higher soluble fractions compared to CE1-2.

[0679] Thus, MC1 and MC2 are able to produce homo-PP with significantly higher catalyst activity with similar characteristics to MC3 known from the literature. This is achieved at low xylene solubles.

[0680] Similar to the findings in ethylene polymerization, in propylene bulk polymerization, IC1 and IC2 showed higher catalyst activity than the comparative example CC1, while M w The performance of MC1 and MC2 was similar to that of MC6. A good powder morphology with spherical polymer particles was obtained. The derived polymer properties of MC1 and MC2, such as isotacticity, soluble components and melting temperature were at comparable levels. MC5 and MC6 (comparative examples) generally showed overall poorer performance under propylene polymerization conditions. For these comparative examples, lower activity catalysts with poor polymer morphology and lower molecular weight and lower isotacticity were obtained.

Claims

1. A racemic metallocene complex of formula (I') wherein each X is a σ-donating ligand; L is a carbon or silicon based divalent bridge in which one or two backbone atoms are linked to the ligand; M is Ti, Zr or Hf; Each Het is independently a monocyclic 5- or 6-membered heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S; Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy, Each n is 1-3; Each R2 is the same or different and is a -Si(RaRbRc) group; Ra is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; Rb is optionally replaced by 1-3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; Rc is optionally replaced by 1-3 C 1-6 Alkyl-substituted phenyl; and Each p is 1-3.

2. A racemic metallocene complex of formula (Ia) wherein each X is a σ-donating ligand; Each Het is independently a monocyclic 5- or 6-membered heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S; L is a (RdRe)Si group or a (RdRe)C group; Rd is C 1-10 Alkyl, C 5-10 cycloalkyl, benzyl or phenyl; Re is C 2-10 Alkenyl or -Si(Me)2; M is Ti, Zr or Hf; Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy, Each n is 1-3; Each R2 is the same or different and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group; Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and Each p is 1-3.

3. The racemic metallocene complex according to claim 2, which is of formula (Ia') wherein each X is a σ-donating ligand; Each Het is independently a monocyclic 5- or 6-membered heteroaromatic or heterocyclic group including at least one heteroatom selected from O, N or S; L is a (RdRe)Si group; Rd is C 1-10 alkyl; Re is C 2-10 alkenyl; M is Ti, Zr or Hf; Each R1 is the same or different and is a straight chain C 1-10 Alkyl or straight chain C 1-10 Alkoxy, Each n is 1-3; Each R2 is the same or different and is C 1-10 Alkyl, C 1-10 Alkoxy or -Si(R)3 group; Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and Each p is 1-3.

4. The racemic metallocene complex of claim 1, wherein L is -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, wherein each R' is independently a hydrogen atom or a C1-C2-containing heteroatom or a fluorine atom of one or more groups 14-16 of the periodic table. 20 A hydrocarbon group, or optionally two R' groups together form a ring.

5. The racemic metallocene complex of claim 1 or 2, wherein L is a (RdRe)Si group, wherein Rd is C 1-10 Alkyl and Re is C 2-10 Alkenyl or -Si(Me)2.

6. The racemic metallocene complex of claim 1 or 2, wherein each Het is independently a monocyclic 5- or 6-membered heteroaromatic or heterocyclic group containing at least one heteroatom selected from O or S.

7. The racemic metallocene complex according to claim 6, wherein the heteroaromatic group or the heterocyclic group contains at least one O heteroatom.

8. The racemic metallocene complex of claim 7, wherein each Het is independently furanyl.

9. The racemic metallocene complex of claim 1 or 2, wherein each R1 is the same or different and is a linear C 1-6 alkyl.

10. The racemic metallocene complex of claim 9, wherein each R1 is methyl.

11. The racemic metallocene complex of claim 1 or 2, wherein each X is independently chlorine, benzyl, cyclohexyl or methyl.

12. The racemic metallocene complex of claim 1 or 2, wherein M is Zr.

13. The racemic metallocene complex of claim 1 or 2, wherein the complex of formula (I') or (Ia) is C2 symmetric.

14. The racemic metallocene complex of claim 1 or 2, wherein n is 1 or 2.

15. The racemic metallocene complex of claim 1 or 2, wherein p is 1.

16. The racemic metallocene complex according to claim 2, which is of formula (XII) wherein each X is a σ-donating ligand; Each Het is independently a monocyclic 5- or 6-membered heteroaryl group including at least one heteroatom selected from O, N or S; L is a (RdRe)Si group; Rd is C 1-10 alkyl; Re is C 2-10 alkenyl; M is Ti, Zr or Hf; Each R1 is the same or different and is a straight chain C 1-10 alkyl; Each n is 1-3; Each R2 is the same or different and is a -Si(R)3 group; Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl; and Each p is 1-3.

17. The racemic metallocene complex of claim 16, wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 -alkyl, C 1-6 - alkoxy, amide, phenyl or benzyl.

18. The racemic metallocene complex of claim 16, wherein each R1 is methyl.

19. The racemic metallocene complex according to claim 2, which is of formula (XII') wherein each X is a σ-donating ligand; L is a (RdRe)Si group; Rd is C 1-10 alkyl; Re is C 2-10 alkenyl; Each R1 is the same or different and is a straight chain C 1-10 alkyl; Each n is 1-3; Each R2 is the same or different and is a -Si(R)3 group; Each R is the same or different and is optionally replaced by 1 to 3 C 1-6 Alkyl substituted C 1-10 Alkyl or phenyl.

20. The racemic metallocene complex of claim 19, wherein each X is independently a hydrogen atom, a halogen atom, a C 1-6 Alkyl, C 1-6 Alkoxy, amide, phenyl or benzyl.

21. The racemic metallocene complex of claim 19, wherein each R1 is methyl.

22. The racemic metallocene complex of claim 1, wherein the complex is Racemic-form.

23. The racemic metallocene complex of claim 2, wherein the complex is Trans-form.

24. A metallocene catalyst comprising: (i) the racemic metallocene complex according to claim 1 or 2; (ii) a promoter comprising a compound of a Group 13 element; and optionally (iii) Vector.

25. The metallocene catalyst of claim 24, wherein the cocatalyst is an aluminoxane.

26. The metallocene catalyst of claim 24 or 25, wherein the support is a porous inorganic support.

27. The metallocene catalyst of claim 26, wherein the support is silica.

28. A method for preparing a metallocene catalyst, comprising contacting a solid support with a cocatalyst solution comprising a compound of a Group 13 element and a racemic metallocene complex as claimed in claim 1 or 2 to form a supported catalyst; or (I) contacting a solid support with a promoter solution comprising a compound of a Group 13 element; thereby forming a support impregnated with the promoter; (II) contacting the support impregnated with the promoter with the racemic metallocene complex as claimed in claim 1 or 2; Thus, a supported catalyst is formed.

29. A process for preparing an olefin polymer, comprising polymerizing at least one olefin in the presence of a metallocene catalyst as claimed in claim 24.

30. The method of claim 29, wherein the olefin polymer is a polyethylene or polypropylene polymer.

31. The method of claim 29, wherein the olefin polymer is optionally comprised of at least one C 4-10 Polyethylene polymers with alpha olefin comonomers.

32. A method for preparing a multimodal polyethylene polymer comprising: (I) In the first stage, ethylene and optionally at least one C 4-10 an alpha olefin comonomer to form a first polyethylene component; (i) the metallocene complex according to claim 1 or 2; (ii) a promoter comprising a compound of a Group 13 element; and optionally (iii) a carrier; (II) in a second stage, polymerizing ethylene and optionally at least one C 4-10 The alpha olefin comonomer is polymerized to form the second polyethylene component.

33. The method of claim 32, wherein the first polyethylene component is a lower molecular weight component, the molecular weight of the lower molecular weight component being in the range of 20,000 to 90,000.

34. The method of claim 33, wherein the molecular weight of the lower molecular weight component is between 60,000 and 90,000.

35. The method of claim 32, wherein the second polyethylene component is a higher molecular weight component, the higher molecular weight component having a molecular weight in the range of 100,000 to 1,000,000.

36. The method of claim 35, wherein the molecular weight of the higher molecular weight component is in the range of 250,000 to 500,000.

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